KR102568266B1 - Purified 2,5-furandicarboxylic acid pathway products - Google Patents

Abstract

The present disclosure provides methods for the purification of 2,5-furandicarboxylic acid (FDCA). The present disclosure further provides crystalline preparations of purified FDCA, as well as methods for their preparation. Moreover, the present disclosure provides mixtures used in methods for the purification of FDCA.

Description

Purified 2,5-furandicarboxylic acid pathway products

Parties to joint research agreement

The disclosed subject matter and claimed invention are covered by a joint research agreement between Rennovia, Inc. and Stora Enso Oyj in effect on and/or prior to the date the claimed invention was made. was made instead of and/or in connection with it, and the claimed invention was made as a result of activities undertaken within the scope of the above agreement.

The present disclosure relates to mixtures and methods for removing impurities from 2,5-furandicarboxylic acid pathway products to produce purified 2,5-furandicarboxylic acid pathway products. In some embodiments, the method comprises reduction and removal of 5-formylfuran-2-carboxylic acid. In some embodiments, the method includes removal of hydroxymethylfurancarboxylic acid. In some embodiments, the mixture includes 5-formylfurancarboxylic acid. In some embodiments, the mixture includes hydroxymethylfurancarboxylic acid.

Furan-2,5-dicarboxylic acid (FDCA) is an industrially important compound. For example, FDCA can be polymerized into industrial quality polyesters. However, the methods used to make FDCA often result in FDCA products containing impurities. These impurities include 5-formylfuran-2-carboxylic acid (FFCA). Impurities can be difficult to remove from FDCA. FDCA products containing impurities can lead to the formation of undesirable color bodies. A color body includes a coloring material and also a precursor to the coloring material (eg, a precursor may be converted to a coloring material during a polymerization reaction). Color bodies are known to form from reaction intermediates or by-products from the oxidation of 5-hydroxymethylfurfural (HMF) during the manufacture of FDCA. A known color-forming impurity is 5-formylfuran-2-carboxylic acid (FFCA), an intermediate structure formed during the oxidation of HMF to FDCA. A need exists for a method of removing impurities from FDCA.

In one aspect, the disclosure provides

A heterogeneous reduction catalyst under conditions sufficient to form a reaction mixture for reducing FDCA pathway products comprising FDCA and 5-formylfurancarboxylic acid (FFCA) to reduce FFCA to hydroxymethylfurancarboxylic acid (HMFCA) and Contacting with hydrogen in the presence of a solvent to produce a purified FDCA pathway product

includes;

The FDCA pathway products purified herein include FDCA, HMFCA, FFCA with less than 10% molar impurity, 5-methyl-2-furoic acid (MFA) with less than 10% molar impurity, and tetrahydrofuran with less than 10% molar impurity. -2,5-dicarboxylic acid (THFDCA);

The solvent is a multi-component solvent comprising water and a water-miscible aprotic organic solvent;

Wherein the heterogeneous reduction catalyst comprises a solid support and a metal selected from the group consisting of Cu, Ni, Co, Pd, Pt, Ru, Ag, Au, Rh, Os, Ir and any combination thereof.

A method for producing a purified 2,5-furandicarboxylic acid (FDCA) pathway product.

A purified FDCA pathway product may contain greater than 90% FDCA on a molar purity basis. A purified FDCA pathway product may contain greater than 95% FDCA on a molar purity basis. A purified FDCA pathway product may contain greater than 99% FDCA on a molar purity basis. The purified FDCA pathway product may include FFCA in a molar purity ranging from 0.1 to 5% or any number in between.

A purified FDCA pathway product may contain less than 5% FFCA on a molar purity basis. A purified FDCA pathway product may contain less than 1% FFCA on a molar purity basis. A purified FDCA pathway product may contain less than 0.5% FFCA on a molar purity basis. A purified FDCA pathway product may contain less than 0.1% FFCA on a molar purity basis. A purified FDCA pathway product may contain less than 0.05% FFCA on a molar purity basis.

The purified FDCA pathway product may include MFA in a molar purity ranging from 0.1 to 5% or any number in between. A purified FDCA pathway product may contain less than 5% MFA on a molar purity basis. The purified FDCA pathway product may contain less than 1% MFA on a molar purity basis. The purified FDCA pathway product may contain less than 0.1% MFA on a molar purity basis.

The purified FDCA pathway product may include THFDCA in a molar purity ranging from 0.1% to 0.9% or any number in between. A purified FDCA pathway product may contain less than 0.9% THFDCA on a molar purity basis. A purified FDCA pathway product may contain less than 0.5% THFDCA on a molar purity basis. A purified FDCA pathway product may contain less than 0.1% THFDCA on a molar purity basis.

The yield of reduced HMFCA from FFCA can be greater than 25%. The yield of reduced HMFCA from FFCA can be greater than 40%. The yield of reduced HMFCA from FFCA can be greater than 75%. The yield of reduced HMFCA from FFCA can be greater than 90%. The yield of reduced HMFCA from FFCA can be greater than 95%. The yield of reduced HMFCA from FFCA can be greater than 99%.

The solid support may be selected from the group consisting of carbon, zirconium dioxide, titanium dioxide, silicon carbide, silicon dioxide, Al ₂ O ₃ , and any combination thereof. The heterogeneous reduction catalyst may further comprise a promoter. The promoter may be selected from the group consisting of Ti, Zr, Cr, Mo, W, Mn, Ru, Cu, Zn, Sb, Bi, Sn, Au, Ag, Pb, Te, and any combination thereof. The solid support may be a shaped porous carbon support. The solid support may be a shaped porous carbon support. The solid support may be zirconium dioxide. The solid support may be titanium dioxide. The solid support may be silicon carbide. The solid support may be a combination of zirconium dioxide and titanium dioxide. The solid support may have a surface area less than 200 m ² /g but non-zero.

Water-miscible aprotic organic solvents are tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketones ("MEK"), and gamma-valerolactone. The water-miscible aprotic organic solvent may be an ether. The water-miscible aprotic organic solvent may be selected from the group consisting of light water-miscible organic solvents and heavy water-miscible organic solvents.

The water and water-miscible aprotic organic solvent may be present in a water:water-miscible organic solvent ratio ranging from 1:6 to 6:1 v/v or any number in between. The water and water-miscible aprotic organic solvent may be present in a water:water-miscible organic solvent ratio within the range defined by 1:6 to 6:1 v/v. The water-miscible aprotic organic solvent may constitute at least 10 vol % of the multi-component solvent. The water-miscible aprotic organic solvent and water may be present in a weight percent ratio of water-miscible aprotic organic solvent:water of 3:2. The water-miscible aprotic organic solvent and water may be present in a weight percent ratio of 4:1 water-miscible aprotic organic solvent:water.

The solvent may be a multi-component solvent comprising water and two different water-miscible organic solvents. The two water-miscible organic solvents may both be water-miscible aprotic organic solvents. Each water-miscible aprotic organic solvent is independently tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP" ), methyl ethyl ketone (“MEK”), and gamma-valerolactone.

The method may be carried out at a temperature of 150 °C or less. The method may be performed at a temperature ranging from 50° C. to 130° C. or any number in between. The process may be conducted at a temperature ranging from 80° C. to 120° C. or any number in between. The method may be conducted at a temperature ranging from 70° C. to 125° C. or any number in between.

The method can be performed at hydrogen pressures ranging from 50 psi to 1000 psi or any number in between. The process can be performed at hydrogen pressures of 100 psi to 500 psi. The process can be performed at hydrogen pressures ranging from 200 psi to 525 psi or any number in between. The method can be performed for 30 minutes or more. The method can be conducted for a period ranging from 30 minutes to 300 minutes or any number of hours in between.

The heterogeneous reduction catalyst and FFCA may be present in a weight percent ratio of heterogeneous reduction catalyst:FFCA ranging from 1:0.001 to 1:1 in the FDCA pathway product. The method can be carried out in a continuous flow reactor.

The method may further include preparing an FDCA pathway product by:

(a) contacting an oxidation feedstock comprising a furanic oxidation substrate and an oxidation solvent with oxygen in the presence of a heterogeneous oxidation catalyst under conditions sufficient to form a reaction mixture for oxidizing the furanic oxidation substrate to an FDCA pathway product; generating an FDCA pathway product;

wherein the FDCA pathway products include FDCA and FFCA;

The reaction mixture is substantially free of added base;

The heterogeneous oxidation catalyst comprises a solid support and a noble metal;

The heterogeneous oxidation catalyst comprises a plurality of pores and a specific surface area ranging from 20 m ² /g to 500 m ² /g or any number therebetween;

The solvent and oxidizing solvent are the same.

Furanic oxidation substrates are selected from the group consisting of 5-(hydroxymethyl)furfural (HMF), diformylfuran (DFF), hydroxymethylfurancarboxylic acid (HMFCA) and formylfurancarboxylic acid (FFCA). can be chosen The oxidizing feedstock may include a furanic oxidizing substrate in a concentration of at least 5% by weight. The furanic oxidizing substrate may be present in a concentration of at least 10% by weight in the oxidizing feedstock. The heterogeneous oxidation catalyst may include a metal loading ranging from 0.3% to 5% by weight of the heterogeneous oxidation catalyst, or any number in between. The heterogeneous oxidation catalyst may further include a promoter. The promoter may be selected from the group consisting of Ti, Zr, Cr, Mo, W, Mn, Ru, Cu, Zn, Sb, Bi, Sn, Au, Ag, Pb, Te, and any combination thereof. The solid support may be a shaped porous carbon support. The solid support may be zirconium dioxide. The solid support may be titanium dioxide. The solid support may be silicon carbide. The solid support may be a combination of zirconium dioxide and titanium dioxide. The solid support may have a surface area less than 200 m ² /g but non-zero.

The method may further include a second oxidation step, wherein the second oxidation step comprises

(b) a second oxidation feedstock comprising a second furanic oxidation substrate and a second oxidation solvent sufficient to form a second reaction mixture for oxidizing the second furanic oxidation substrate to produce a second FDCA pathway product; contacting with oxygen in the presence of a second heterogeneous oxidation catalyst under conditions and producing a second FDCA pathway product.

contains;

wherein the second FDCA pathway product comprises FDCA and FFCA;

(first) contacting step (a) produces a first FDCA pathway product that is an FDCA pathway intermediate compound alone or together with FDCA;

The second furanic oxidation substrate is the first FDCA pathway product;

the second reaction mixture is substantially free of added base;

The second heterogeneous oxidation catalyst comprises a second solid support and a second noble metal which may be the same as or different from the (first) noble metal in step (a);

The second heterogeneous oxidation catalyst includes a plurality of pores and a specific surface area ranging from 20 m ² /g to 500 m ² /g or any number in between.

The method may further include crystallizing the purified FDCA product to produce FDCA having a molar purity greater than 99%. The method may further include crystallizing the purified FDCA product to produce FDCA having a molar purity greater than 99.5%. The method may further include crystallizing the purified FDCA product to produce FDCA having a molar purity greater than 99.8%. The method may further include crystallizing the purified FDCA product to produce FDCA having a molar purity greater than 99.9%.

Crystallization of the purified FDCA product may comprise dissolving the purified FDCA product in a first crystallization solution, wherein the first crystallization solution comprises a crystallization solvent, wherein the crystallization solvent is water and a crystallization water miscible aprotic organic solvent. includes Crystallizing water-miscible aprotic organic solvents are tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketone (“MEK”), and gamma-valerolactone. The crystallizing water-miscible aprotic organic solvent may be an ether. The crystallizing water-miscible aprotic organic solvent and water may be present in a weight percent ratio of 3:2 crystallizing water-miscible aprotic organic solvent:water. The crystallized water-miscible aprotic organic solvent and water may be present in a weight percent ratio of 4:1 water-miscible aprotic organic solvent:water. The purified FDCA product is defined by 110-120°C (e.g., 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, or 120°C or any two of the aforementioned temperatures. temperature within the range) may be dissolved in the first crystallization solution. The purified FDCA product may be dissolved in the first crystallization solution at a temperature of 110 to 115 °C. The purified FDCA product may be dissolved in the first crystallization solution at a temperature of 120°C. Crystallization of the purified FDCA product may further comprise dissolving the purified FDCA product in a second crystallization solution, wherein the second crystallization solution comprises a crystallization solvent, wherein the crystallization solvent is water and the crystallization water miscible aprotic Contains organic solvents. Crystallizing the purified FDCA product may further comprise dissolving the purified FDCA product in any number of subsequent crystallization solutions (e.g., a third, fourth, fifth or sixth crystallization solution); wherein the second crystallization solution comprises a crystallization solvent, wherein the crystallization solvent comprises water and a crystallization water-miscible aprotic organic solvent.

In another aspect, the present disclosure provides FDCA, HMFCA, FFCA of less than 10% molar impurity, 5-methyl-2-furoic acid (MFA) of less than 10% molar impurity, and tetra purified 2,5-furandicarboxylic acid (FDCA) pathway products including hydrofuran-2,5-dicarboxylic acid (THFDCA);

a heterogeneous reduction catalyst comprising a solid support and a metal selected from the group consisting of Cu, Ni, Pd, Pt, Ru, Ag, Au, Rh, Os, Ir, and any combination thereof; and multi-component solvents including water and water-miscible aprotic organic solvents.

It relates to a mixture containing

The mixture may further contain hydrogen. The purified FDCA pathway product may contain less than 10% molar impurity of 2,5-diformylfuran (DFF). The solid support may be selected from the group consisting of carbon, zirconium dioxide, silicon carbide, silicon dioxide, and Al ₂ O ₃ , any combination thereof. The heterogeneous reduction catalyst may be selected from the group consisting of Cu/SiO ₂ , Cu/Mn/Al ₂ O ₃ , Ni/Al ₂ O ₃ , Pd/C, Ru/C, and any combination thereof. The solid support may be a shaped porous carbon support. The solid support may have a surface area less than 200 m ² /g but non-zero.

FFCA and FDCA may be at least partially soluble in multi-component solvents. Water-miscible aprotic organic solvents are tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP"), methyl ethyl ketones ("MEK"), and gamma-valerolactone. The water-miscible aprotic organic solvent may be selected from the group consisting of light water-miscible organic solvents and heavy water-miscible organic solvents. The water and water-miscible aprotic organic solvent may be present in a water:water-miscible organic solvent ratio ranging from 1:6 to 6:1 v/v or any number in between. The water and water-miscible aprotic organic solvent may be present in a water:water-miscible organic solvent ratio within the range defined by 1:6 to 6:1 v/v. The water and water-miscible aprotic organic solvent may be present in a water:water-miscible aprotic organic solvent ratio of 1:1 v/v. The water-miscible aprotic organic solvent may constitute at least 10 vol % of the multi-component solvent. The water-miscible aprotic organic solvent and water may be present in a weight percent ratio of water-miscible aprotic organic solvent:water of 3:2. The water-miscible aprotic organic solvent and water may be present in a weight percent ratio of 4:1 water-miscible aprotic organic solvent:water.

Multi-component solvents can include water and two different water-miscible organic solvents. Each water-miscible aprotic organic solvent is independently tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP" ), methyl ethyl ketone (“MEK”), and gamma-valerolactone.

Figure 1 shows the selectivity of the reduction of FFCA to HMFCA using different catalysts, different temperatures and different reaction times.
Figure 2 shows the reduction of FFCA to HMFCA and MFA using different catalysts, different temperatures and different reaction times.
Figure 3 shows the reduction of FDCA to THFDCA using different catalysts, different temperatures and different reaction times.
Figure 4 shows the selectivity of reduction to HMFCA in mixtures of FDCA and FFCA using different catalysts, different temperatures and different reaction times, where the percentage of FDCA remaining is for each reduction shown.
Figure 5 shows the reduction to HMFCA, MFA and THFDCA in a mixture of FDCA and FFCA using different catalysts, different temperatures and different reaction times.
Figure 6 shows the selectivity of reduction of mixtures of FDCA and FFCA using different catalysts, different catalyst amounts, different temperatures, different reaction times and different pressures.
Figure 7 shows the distribution of products and mass balances from reduction to HMFCA, MFA and THFDCA in mixtures of FDCA and FFCA using different catalysts, different catalyst amounts, different temperatures, different reaction times and different pressures.
Figure 8 shows the distribution of products and mass balances from reduction to HMFCA, MFA and THFDCA in mixtures of FDCA and FFCA using Cu T-4874 as catalyst, different catalyst amounts, different temperatures and different pressures.
Figure 9 shows the distribution of product and mass balance for reduction to HMFCA, MFA and THFDCA in mixtures of FDCA and FFCA using Pd/C JM-9 as catalyst, different catalyst amounts, different reaction times and different temperatures.
10 shows the distribution of products and mass balances for reducing a mixture of FDCA and FFCA to HMFCA, MFA and THFDCA using Pd/C JM-10 as catalyst, different catalyst amounts, different reaction times and different temperatures.
Figure 11 shows the distribution of product and mass balance for reduction to HMFCA, MFA and THFDCA in a mixture of FDCA and FFCA using Ru/C JM-37 ^* as catalyst, different catalyst amounts, different reaction times and different temperatures. .
Figure 12 shows the distribution of product and mass balance for reduction to HMFCA, MFA and THFDCA in a mixture of FDCA and FFCA using Ru/C JM-38 ^* as catalyst, different catalyst amounts, different reaction times and different temperatures. .
13-20 show products, mass balance and space time yields for oxidation of HMF substrates using various ratios of Bi/Pt, different catalytic amounts, different amounts of Pt, and different amounts of Bi on carbon black, zirconia and montmorillonite supports as catalysts. The distribution of (STY) is shown.
Figures 21-28 show the distributions of product, mass balance and space time yield (STY) for oxidation of HMF substrates using various ratios of Bi/Pt titania supports as catalysts, different amounts of Pt and different amounts of Bi.
29-36 show distributions of product, mass balance and space time yield (STY) for oxidation of HMF substrates using Pt and Bi/Pt catalysts, different amounts of Pt and different amounts of Bi on various zirconia supports as catalysts. .
37-44 show products, mass balance and space for oxidation of HMF substrates using Pt and Bi/Pt catalysts on various tungstated titania and zirconia supports as catalysts, different amounts of Pt, different amounts of Bi, and different support treatments. The distribution of time yield (STY) is shown.
Figures 45-47 show the distribution of product and metal leaching for fixed bed oxidation of HMF substrates using Pt catalysts on zirconia supports with various reaction conditions.
Figures 48-50 show the distributions of product, space time yield (STY), and metal leaching for fixed bed oxidation of HMF substrates using Bi/Pt catalysts on zirconia supports with various reaction conditions.
51-55 show Pt/Bi, Pt/Te and Pt/Sn catalysts on various carbon, carbon/ZrO ₂ , TiO ₂ , ZrO _{2 , ZrO 2} /TiO ₂ , SiC, and TiC—SiC supports as catalysts, different amounts of Pt. , and distributions of product and mass balances for the oxidation of HMF substrates using different amounts of Bi.
56-58 show the distribution of product, space time yield (STY), and metal leaching for fixed bed oxidation of HMF substrates using small particle Bi/Pt catalysts on zirconia support with various reaction conditions.
59-60 show distributions of product and space time yield (STY) for fixed bed oxidation of HMF substrates using small particle Bi/Pt catalysts on zirconia/titania supports with various reaction conditions.
61-68 show distributions of product, mass balance and space time yield (STY) for oxidation of HMF substrates using Pt, Pt/Bi, Pt/Te and Pt/Sn catalysts on various supports.

I. Methods of Making FDCA Pathway Products

Methods of making FDCA pathway products are described in International Application No. PCT/US17/13197 by Sokolovskii et al., which is expressly incorporated herein by reference in its entirety, by Rennovia and Stora Enso. ) is described by

In one embodiment, the present disclosure provides a method for preparing furandicarboxylic acid (FDCA) pathway products from oxidation of a furanic oxidizing substrate. As used herein, the terms “furandicarboxylic acid pathway product” and “FDCA pathway product” refer to 2,5-furandicarboxylic acid (FDCA) or 2,5-furandicarboxylic acid pathway intermediate compounds. Used interchangeably to refer to The term "furandicarboxylic acid pathway" is used herein to refer to the pathway shown in Scheme 1, which represents the conversion of HMF (Compound I) to FDCA (Compound V). As used herein, the terms “2,5-furandicarboxylic acid pathway intermediate compound” and “FDCA pathway intermediate compound” refer to diformylfuran corresponding to compounds II, III, and IV in Scheme 1, respectively. (DFF), hydroxymethylfurancarboxylic acid (HMFCA), and 5-formylfurancarboxylic acid (FFCA).

Scheme 1: Furandicarboxylic acid pathway

This disclosure,

(a) contacting an oxidation feedstock comprising a furanic oxidation substrate and an oxidation solvent with oxygen in the presence of a heterogeneous oxidation catalyst under conditions sufficient to form a reaction mixture for oxidizing the furanic oxidation substrate to an FDCA pathway product; Generating FDCA pathway products

Including,

wherein the oxidation solvent is a solvent selected from the group consisting of organic solvents and multi-component solvents, the reaction mixture is substantially free of added base, and the heterogeneous oxidation catalyst comprises a solid support and a noble metal;

The heterogeneous oxidation catalyst has a plurality of pores and a range of 20 m ² /g to 500 m ² /g or any number in between, such as 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500 m ² /g, or as defined by any two surface areas mentioned above Including the specific surface area within the range,

Methods for producing FDCA pathway products from furanic oxidized substrates.

The term "substantially free of added base" is used herein to refer to the absence of any base added to the reaction mixture (i.e., no base added), or the addition of a minimum acceptable amount of base. . The term "minimum acceptable amount of base" is used herein when added to a reaction mixture used in the practice of the present disclosure, compared to the same oxidation reaction performed under identical conditions except that no base was added to the reaction mixture. It is used to refer to the amount of base that does not alter the oxidation reaction by more than 1% in terms of product yield or product selectivity. Typically, the methods of the present disclosure are performed under base-free conditions, eg, no base is added to the reaction mixture during the contacting (ie, oxidation) step.

The oxidation methods of the present disclosure can produce the desired FDCA pathway products in yields that are typically at least 80% and with selectivities that are typically at least 90% (both on a molar basis). In some embodiments, the yield is at least 85%, in other embodiments it is at least 90%, at least 95%, and often at least 98% or at least 99%. In some embodiments, the yield ranges from 85 to 90%, 87 to 92%, 90 to 95%, 92 to 97%, 95 to 98%, or 97 to 99%, or to any two percentages noted above. within the range defined by The selectivity for the production of the desired FDCA pathway product is more typically at least 91% or at least 92% or at least 93% or at least 94% or at least 95% or at least 96% or at least 97% or at least 98% or at least 99%. . In some embodiments, the selectivity for the production of the desired FDCA pathway product is between 91 and 93%, 92 and 94%, 93 and 95%, 94 and 96%, 95 and 97%, 96 and 98%, 97 and 99% is in the range of, or within the range defined by any two percentages noted above. The desired FDCA pathway product is usually FDCA.

The term “oxidation feedstock” is used herein to refer to a source material for a furanic oxidation substrate. As used herein, the term "furanic oxidation substrate" refers to a compound that is an HMF or FDCA intermediate compound (eg, DFF, HMFCA, or FFCA, or a combination thereof) or a combination thereof. The oxidizing feedstock used in the practice of the methods described herein may be used in any of a variety of forms, including, for example, solutions, suspensions, dispersions, emulsions, and the like. Typically, the oxidation feedstock comprises a furanic oxidation substrate in solution with an oxidation solvent.

In the oxidation methods described herein, the FDCA pathway products typically include FDCA. In certain embodiments, the furanic oxidizing substrate typically includes HMF. However, it may be desirable to use a furanic oxidation substrate that is an FDCA pathway intermediate compound or a mixture of FDCA pathway intermediate compounds, for example DFF, HMFCA, or FFCA, or a mixture of any two or more thereof. This may be an attractive option in situations where HMF has previously been oxidized to an FDCA pathway intermediate compound or mixture of intermediate compounds, and the intermediate compound(s) are available for use as raw materials. When such an intermediate is used as a furanic oxidation substrate in the oxidation method of the present disclosure, the resulting FDCA pathway product typically includes FDCA, but it is also "in the FDCA pathway" of the FDCA pathway intermediate used as a furanic oxidation substrate. It may include different FDCA pathway intermediate compounds "downstream" (from an oxidation point of view).

The oxidation feedstock may contain other agents or other components that are soluble or insoluble in the oxidation feedstock. For example, the oxidation feedstock can be HMF, or a crude oxidation feedstock of another furanic oxidation substrate, and an oxidation solvent. As used herein, the term "crude feedstock" refers to a feed that, in addition to containing the desired furanic oxidation substrate, also includes impurities and/or by-products associated with the production, isolation, and/or purification of the desired furanic oxidation substrate. refers to raw materials. For example, the oxidized feedstock is further derived from biomass or produced from biomass to sugar conversion (eg, by thermal, chemical, mechanical, and/or enzymatic degradation means). It may contain certain biomass-related components that are by-products, where these sugars are then converted to HMF. Thus, the oxidizing feedstock may also include various polysaccharides and/or polysaccharide-containing mixtures (e.g., materials or mixtures comprising or consisting of cellulose, lignocellulose, hemicellulose, starch, oligosaccharides such as , raffinose, maltodextrin, cellodextrin, monosaccharides such as glucose, fructose, galactose, mannose, xylose, rabinose, disaccharides such as sucrose, lactose, maltose, cellobiose, furan based substrates such as furfural, oligomeric or polymeric humin by-products (humins) and/or remaining mineral acids or any mixtures thereof.Similarly, the oxidized feedstock may be selected from HMF and/or FDCA pathway intermediate compounds It may be a crude feedstock for HMF oxidation products including

In addition to exhibiting high yields and high selectivity, the oxidation methods provided in this disclosure produce FDCA pathway products, such as FDCA, in relatively high concentrations in the resulting product solutions. The high productivity levels obtained from the processes described herein are believed to be due to the combination of the heterogeneous oxidation catalysts used and the nature of the oxidation solvents.

As used herein, the term “oxidation solvent” refers to an organic solvent in which the furanic oxidation substrate and the desired FDCA pathway product are separately soluble at a minimum level of at least 2% by weight at the temperature at which the contacting (oxidation) step is performed. or a solvent that is a multi-component solvent. Typically, the oxidation solvent comprises at least 3%, at least 4%, and more typically, at least 5%, at least 6%, at least 7% by weight of the FDCA pathway product, measured at the temperature at which the contacting step is performed. %, at least 8%, at least 9%, at least 10%, at least 11%, at least 12%, at least 13%, at least 14%, or at least 15% or any two solubilities noted above It has a solubility within the range defined by In some embodiments, the FDCA pathway product is 2 to 4%, 3 to 5%, 4 to 6%, 5 to 7%, 6 to 8%, 7 to 9%, 8 to 10% by weight , 9 to 11%, 10 to 12%, 11 to 13%, 12 to 14%, or 13 to 15%, or within the range defined by any two solubilities noted above. have The solubility of FDCA pathway products in candidate organic solvents or candidate multi-component solvents can be readily determined using known methods.

While not wishing to be bound by theory, the oxidation solvents used in the present disclosure provide efficient conversion of furanic oxidation substrates to FDCA pathway products (this disclosure catalyzed by a high-performance catalyst of the content) is believed to facilitate. In addition, the relatively high concentrations of FDCA and FDCA intermediate compounds achievable in the methods of the present disclosure include, for example, methods using poor solvents such as water or acetic acid-water mixtures described in U.S. Patent No. 7,700,788. In contrast, it provides high process productivity and more expensive solvent removal. Accordingly, the present disclosure provides a particularly attractive method for commercial scale production of FDCA and related intermediates.

In carrying out the oxidation methods of the present disclosure, the furanic oxidizing substrate may be present in the oxidizing feedstock in any concentration up to its solubility limit, in situations where the feedstock is in solution. In some embodiments, the concentration of the furanic oxidation substrate in the oxidation feedstock is at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, by weight of the oxidation feedstock. at least 7%, at least 8%, at least 9%, at least 10%, at least 11%, at least 12%, at least 13%, at least 14%, or at least 15%, or within the range defined by any two concentrations mentioned above. In some embodiments, the concentration of the furanic oxidation substrate in the oxidized feedstock is 1 to 3%, 2 to 4%, 3 to 5%, 4 to 6%, 5 to 7%, 6 to 8% by weight. %, 7 to 9%, 8 to 10%, 9 to 11%, 10 to 12%, 11 to 13%, 12 to 14%, or 13 to 15%, or within the range defined by any two weight percentages recited. Typically, the furanic oxidizing substrate is present in the oxidizing feedstock in a concentration of at least 5% by weight. More typically, the furanic oxidizing substrate is present in an amount of at least 6% by weight, or at least 7% by weight, or at least 8% by weight, or at least 9% by weight, or at least 10% by weight, or at least at the temperature at which the catalytic (oxidation) step is performed. present in the oxidized feedstock at a concentration of 11%, or at least 12%, or at least 13%, or at least 14%, or at least 15% by weight or within a range defined by any two concentrations noted above there is. In some embodiments, the furanic oxidized substrate is present at the temperature at which the catalytic (oxidation) step is performed in an amount of 6 to 8%, 7 to 9%, 8 to 10%, 9 to 11%, 10 to 12%, present in the oxidizing feedstock at a concentration ranging from 11 to 13%, 12 to 14%, or 13 to 15%, or within a range defined by any two of the aforementioned weight%.

Organic solvents that exhibit the minimum solvation requirements necessary for furanic oxidizing substrates and FDCA are suitable for use in the practice of the present disclosure, either alone or as components of multi-component solvents. In particular, it has been found that the use of an aprotic organic solvent in combination with the catalysts and conditions described herein appears to facilitate the high productivity exhibited for the methods of the present disclosure. Thus, in some embodiments, the oxidation solvent includes an aprotic organic solvent (eg, an ether, ester, or ketone) either alone (eg, as a single component solvent) or as a component of a multi-component solvent. When used in multi-component solvents, aprotic organic solvents are typically miscible with the other component(s) of the multi-component solvent. The term “multi-component solvent” herein refers to a mixture of two, three, or more solvent species. A multi-component solvent used in the practice of the present disclosure may include a first organic solvent species, a second organic solvent species, or two or more solvent species selected from water. When the multi-component solvent includes water and an organic solvent, the organic solvent is a water-miscible organic solvent. Typically, the water-miscible organic solvent is a water-miscible aprotic organic solvent.

Exemplary multi-component solvents that exhibit this effect include those comprising water and water-miscible aprotic organic solvents. Exemplary water-miscible aprotic solvents suitable for use in the practice of the present disclosure include tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2- pyrrolidone ("NMP"), methyl ethyl ketone ("MEK"), and/or gamma-valerolactone. Preferably, the water-miscible aprotic organic solvent is an ether such as, for example, glyme, dioxane (1,4-dioxane), dioxolane (eg 1,3-dioxolane), or tetrahydro it's furan Glymes suitable for use in the practice of the present disclosure include, for example, monoglyme (1,2-dimethoxyethane, “DME”), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, tri glyme, butyl diglyme, tetraglyme, polyglyme, and/or highly ethoxylated diethers of high molecular weight alcohols ("hyglyme"). Often, the oxidation solvent is a multi-component solvent comprising water and a water-miscible aprotic organic solvent that is glyme, diglyme, or dioxane.

Organic solvents and multi-component solvents suitable for use as oxidation solvents in the practice of this disclosure are disclosed in PCT Application No. PCT/US17/13197, Renovia and Stora Enso, as previously mentioned, expressly incorporated herein by reference in their entirety. and can be readily identified as described.

In some embodiments, the composition of the oxidation solvent is adjusted to further downstream processes (e.g., to facilitate product recovery, purification, etc., such as to make a purified FDCA pathway product described herein), or upstream The requirements of the process (eg, conversion of sugars to furanic oxidizing substrates) can be taken into account.

In some embodiments, it may be desirable to use an oxidation solvent that is a multi-component solvent comprising a light solvent and a heavy solvent. The term “light solvent” refers to a solvent that has a boiling point at a particular pressure that appears at a temperature lower than the boiling point (boiling temperature) of a heavy solvent at the same pressure. Conversely, the term “heavy solvent” refers to a solvent that has a boiling point at a particular pressure which appears at a temperature higher than the boiling point (boiling temperature) of a light solvent at the same pressure. When the multi-component solvent includes water and a water-miscible organic solvent, the water-miscible organic solvent may be a light water-miscible organic solvent (eg, a water-miscible organic solvent having a boiling point occurring at a temperature lower than that of water), or It may be a heavy water-miscible organic solvent (eg, a water-miscible organic solvent having a boiling point occurring at a temperature higher than the boiling point of water). Typically, the light and heavy water-miscible organic solvents are light and heavy aprotic organic solvents, respectively. Exemplary light water-miscible (and aprotic) organic solvents used with water in multi-component solvents include, for example, glyme, dioxolane (e.g., 1,3-dioxolane), or tetrahydrofuran. include Exemplary heavy water-miscible (and aprotic) organic solvents used with water in multi-component solvents include, for example, dioxane, ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme , butyl diglyme, tetraglyme, or polyglyme. In some embodiments (eg, continuous reactor systems), all or a portion of the oxidation solvent or components thereof may be removed from the product solution (eg, by distillation) and recycled to the reaction mixture. In such an embodiment, a composition corresponding to or capable of forming an azeotropic mixture at the temperature used during the oxidation step (eg, the contacting step), or at the temperature used during a process upstream or downstream of the oxidation step ( For example, it may be desirable to use a multi-component solvent having an "azeotropic composition"). The use of such a multi-component solvent with an azeotrope composition can facilitate recycling of the oxidation solvent (as part of the azeotrope composition) to the oxidation step, or to processes occurring upstream and/or downstream of the oxidation step.

In some embodiments, the water-miscible organic solvent species comprises at least 5 vol %, at least 10 vol %, at least 15 vol %, at least 20 vol %, at least 25 vol %, at least 30 vol %, at least 35 vol%, at least 40 vol%, at least 45 vol%, at least 50 vol%, at least 55 vol%, at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, at least 80 vol%, at least 85 vol %, at least 90 vol %, or at least 95 vol % or within the range defined by any two volume % mentioned above; Correspondingly, water typically represents less than 95 vol%, less than 90 vol%, less than 85 vol%, less than 80 vol%, less than 75 vol%, less than 70 vol%, less than 65 vol%, 60 vol% of the multicomponent system, respectively. Less than 55 vol%, Less than 50 vol%, Less than 45 vol%, Less than 40 vol%, Less than 35 vol%, Less than 30 vol%, Less than 25 vol%, Less than 20 vol%, Less than 15 vol%, 10 vol% less than, or less than 5 vol % (but not zero) or within a range defined by any two volume % mentioned above (but not both).

In some embodiments, the multi-component solvent comprises water in the range of 1-5% by weight or any number in between and water miscible organic solvent in the range of 99-95% by weight or any number in between. In some embodiments, the multi-component solvent comprises water in the range of 5-10% by weight or any number in between and water miscible organic solvent in the range of 5-10% by weight or any number in between. In some embodiments, the multi-component solvent comprises water in the range of 10-15% by weight or any number therebetween and water miscible organic solvent in the range of 90-85% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 15-20% by weight or any number therebetween and water miscible organic solvent in the range of 85-80% by weight or any number in between. In some embodiments, the multi-component solvent comprises water in the range of 20-25% by weight or any number therebetween and water miscible organic solvent in the range of 80-75% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 25-30% by weight or any number therebetween and water miscible organic solvent in the range of 75-70% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 30-35% by weight or any number therebetween and water miscible organic solvent in the range of 70-65% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 35-40% by weight or any number therebetween and water miscible organic solvent in the range of 65-60% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 40-45% by weight or any number therebetween and water miscible organic solvent in the range of 60-55% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 45-50% by weight or any number therebetween and water miscible organic solvent in the range of 65-50% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 50-55% by weight or any number therebetween and water miscible organic solvent in the range of 50-45% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 55-60% by weight or any number therebetween and water miscible organic solvent in the range of 45-40% by weight or any number in between. In some embodiments, the multi-component solvent comprises water in the range of 60-65% by weight or any number therebetween and water miscible organic solvent in the range of 40-35% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 65-70% by weight or any number therebetween and water miscible organic solvent in the range of 35-30% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 70-75% by weight or any number therebetween and water miscible organic solvent in the range of 30-25% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 75-80% by weight or any number therebetween and water miscible organic solvent in the range of 25-20% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 80-85% by weight or any number therebetween and water miscible organic solvent in the range of 20-15% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 85-90% by weight or any number therebetween and water miscible organic solvent in the range of 15-10% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 90-95% by weight or any number therebetween and water miscible organic solvent in the range of 10-5% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 95-99% by weight or any number therebetween and water miscible organic solvent in the range of 5-1% by weight or any number therebetween.

In some embodiments, the volume ratio of water to water miscible organic solvent ranges from 1:6 to 6:1 or any number in between. In certain embodiments, the volume ratio is in the range of 1:4 to 4:1, or any number of water:water miscible organic solvents in between. In another embodiment, the volume ratio is in the range of 1:4 to 3:1 or any number of water:water miscible organic solvents in between. In another embodiment, the volume ratio is in the range of 1:3 to 3:1 or any number of water:water miscible organic solvents in between. In certain embodiments, the volume ratio is 1:1 water:water miscible organic solvent.

In some embodiments, the multi-component solvent includes water and two different water-miscible organic solvents. Typically both water-miscible organic solvents are water-miscible aprotic organic solvents. The two water-miscible aprotic solvents are each independently tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP "), methyl ethyl ketone ("MEK"), and/or gamma-valerolactone. One or both of the water-miscible aprotic organic solvents may be ethers such as, for example, glyme, dioxane (eg 1,4-dioxane), dioxolane (eg 1,3-dioxane) solan), tetrahydrofuran, and the like. Glyme is, for example, monoglyme (1,2-dimethoxyethane, “DME”), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglyme, and/or highly ethoxylated diethers of high molecular weight alcohols ("hyglymes").

In some embodiments, the volume ratio of water to the first and second water-miscible organic solvents is approximately 1:1:1 (v:v:v). In some embodiments, the volume ratio of water to the first and second water-miscible organic solvents is approximately 1:2:1 (v:v:v). In some embodiments, the volume ratio of water to the first and second water-miscible organic solvents is approximately 1:2:2 (v:v:v). In some embodiments, the volume ratio of water to the first and second water-miscible organic solvents is approximately 2:1:1 (v:v:v).

In some embodiments, the multi-component solvent comprises water and two different water-miscible organic solvents in relative amounts of water to first and second water-miscible organic solvents. Suitable multi-component solvents, including water and two different water-miscible organic solvents, are disclosed in PCT Application No. PCT/US17/13197 by Renovia and Stora Enso, expressly incorporated herein by reference in their entirety as previously mentioned. is described by

The contacting step often comprises at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, at least 7%, at least 8%, at least 9%, by weight, of the (soluble) FDCA pathway product. %, at least 10%, at least 11%, at least 12%, at least 13%, at least 14%, or at least 15% by weight, or within a range defined by any two values noted above. and for a period of time sufficient to produce a product solution comprising the concentration. Correspondingly, when a product solution comprising (soluble) FDCA pathway product is produced, it is at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, at least 7%, at a concentration of at least 8%, at least 9%, at least 10%, at least 11%, at least 12%, at least 13%, at least 14%, or at least 15%, or any of the aforementioned It is produced at a concentration within the range defined by the two values. The term "product solution" as used herein refers to a solution of the soluble FDCA pathway product and other soluble components of the reaction mixture in an oxidation solvent. The phrase “time sufficient to produce a product solution comprising an FDCA pathway product at a concentration of” refers herein to the minimum amount of time required to produce a specified concentration of an FDCA pathway product in a product solution.

Heterogeneous oxidation catalysts used in the practice of the present disclosure typically have noble metals dispersed on the inner and outer surfaces of the support. The term "noble metal" as used herein refers to ruthenium, rhodium, palladium, silver, osmium, iridium, platinum or gold or mixtures thereof. In certain preferred embodiments, the metal is selected from platinum, or gold, or combinations thereof. In some embodiments, the metal is platinum. In some embodiments, the metal is gold. The heterogeneous oxidation catalyst may further include a promoter to enhance the performance of the heterogeneous oxidation catalyst. Suitable promoters may include Ti, Zr, Cr, Mo, W, Mn, Ru, Cu, Zn, Sb, Bi, Sn, Au, Ag, Pb, or Te or mixtures thereof. When the metal is platinum, or gold, or combinations thereof, suitable accelerators include, for example, Bi, Te, Sn, Pd, Ir, Mo, or W or mixtures thereof. In some embodiments, the accelerator is Bi. In some embodiments, the accelerator is Te. In some embodiments, the accelerator is Sn.

Heterogeneous oxidation catalysts typically include a noble metal at a total metal loading ranging from 0.3% to 5% by weight or any number in between. In some embodiments, the metal loading ranges from 0.5% to 4% by weight or any number in between. In some embodiments, the metal loading is in the range of 2 to 4 weight percent or any number in between. In some embodiments, the metal loading is 2% by weight. In some embodiments, the metal loading is 3% by weight. In some embodiments, the metal loading is 4% by weight. When two or more metals are used, the heterogeneous oxidation catalyst may comprise a plurality of heterogeneous oxidation catalyst particles each comprising two or more metals, or the heterogeneous oxidation catalyst may comprise a heterogeneous oxidation catalyst metal-particle species; For example, it may include a mixture of a first plurality of heterogeneous oxidation catalyst particles comprising a first metal species and a second plurality of heterogeneous oxidation catalyst particles comprising a second metal species. Methods for preparing heterogeneous oxidation catalysts used in the practice of this disclosure are described by Renovia and Stora Enso in PCT Application No. PCT/US17/13197, expressly incorporated herein by reference in its entirety, as previously noted. are listed.

The solid support component of the heterogeneous oxidation catalyst may include any type of material known by those skilled in the art to be suitable for use as a catalyst support, also having the specific surface area requirements described herein. Suitable materials include, for example, metal oxides, carbonaceous materials, polymers, metal silicates, metal carbides, or any composite material made therefrom. Exemplary metal oxides include silicon oxide (silica), zirconium oxide (zirconia), titanium oxide (titania), titanium dioxide or aluminum oxide (alumina). As used herein, the term "carbonaceous" refers to graphite and carbon black, which may or may not be in an activated form. Exemplary metal silicates include, for example, orthosilicates, borosilicates, or aluminosilicates (eg, zeolites). Exemplary metal carbides include, for example, silicon carbide. Suitable polymeric solid support materials include polystyrene, polystyrene-co-divinyl benzene, polyamide, or polyacrylamide.

Suitable solid support materials also include composite materials made from or comprising a binder and a material selected from metal oxides, carbonaceous materials, polymers, metal silicates and/or metal carbides. In some embodiments, the binder is a resin. In another embodiment, the composite material comprises a carbonized binder and a material selected from metal oxides, carbonaceous materials, metal silicates and/or metal carbides. In one embodiment, the composite material includes a carbonized binder and carbon black, which may or may not be or include activated carbon. Methods for making such carbon-based composite materials are described by Dias et al., by Renovia in PCT Application No. PCT/US15/28358, expressly incorporated herein by reference in its entirety.

In some embodiments, the solid support is Aditya Birla CDX-KU, Aditya Birla CSCUB, Aditya Birla R2000B, Aditya Birla R2500UB, Aditya Birla R3500B, Aditya Birla R3500B Tiya Birla R5000U2, Arosperse 5-183A, Asbury 5302, Asbury 5303, Asbury 5345, Asbury 5348R, Asbury 5358R, Asbury 5365R, Asbury 5368, Asbury 5375R, Asbury 5379, Asbury A99, Cabot Monarch 120, Cabot Monarch 280, Cabot Monarch 570, Cabot Monarch 700, Cabot Norit Darco 12x20L1, Cabot Vulcan Vulcan XC72, Continental N120, Continental N234, Continental N330, Continental N330-C, Continental N550, Norit ROX 0.8, Orion Arosperse 138, Orion Arosperse 15, Orion Color Black ( Orion Color Black) FW 2, Orion Color Black FW 255, Orion HiBlack 40B2, Orion Hi-Black 50 L, Orion Hi-Black 50 LB, Orion Hi-Black 600 L, Orion HP-160, Orion Lamp Orion Lamp Black 101, Orion N330, Orion Printex L6, Sid Richardson Ground N115, Sid Richardson Ground SR155, Sid Richardson SC159, Sid Richardson SC419, Timkal Ensaco (Timcal Ensaco) 150G, Timcal Ensaco 250G, Timcal Ensaco 260G, and/or Timcal Ensaco 350G or any combination thereof.

Metal impregnation of the solid support typically causes negligible changes in the specific surface area, pore diameter, and specific volume of the solid support. Heterogeneous oxidation catalysts suitable for use in the present disclosure typically have a plurality of pores and pores in the range of, for example, 20 m ² /g to 500 m ² /g, such as 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500 m ² /g, or any of the aforementioned It is prepared using a solid support having a specific surface area within the range defined by the two surface areas. The specific surface area is measured using known methods such as Brunauer, Emmett and Teller (J. Am. Chem. Soc. 1938, 60:309-311) and/or mercury porosimetry It can be. See, eg, ASTM test methods D3663, D6556, and D4567, each of which is incorporated by reference in its entirety. Typically, the heterogeneous oxidation catalyst (and solid support) used in the practice of the present disclosure ranges from 25 m ² /g to 250 m ² /g or any number in between, also sometimes from 25 m 2 /g to 225 m ² /g. in the range of m ² /g or any number in between, or in the range of 25 m ² /g to 200 m ² /g or any number in between, or in the range of 25 m ² /g to 175 m ² /g or in between , or in the range of 25 m ² /g to 150 m ² /g or any number in between, or in the range of 25 m ² /g to 125 m ² /g or any number in between, or 25 m ² /g to 100 m ² /g or any number in between. These specific surface areas are relatively low compared to highly porous catalyst support materials more typically used in the art, such as, for example, activated carbon. The relatively low surface area of the heterogeneous oxidation catalyst used in the oxidation process of the present disclosure advantageously contributes to the high selectivity and yield exhibited for the conversion of furanic oxidation substrates to FDCA and FDCA pathway intermediate compounds under substantially base-free conditions. It is considered to be

Heterogeneous oxidation catalysts (and solid support components thereof) used in the practice of the present disclosure, commensurate with relatively low specific surface areas, also typically have relatively moderate to low specific pore volumes compared to other oxidation catalysts. Heterogeneous oxidation catalysts (and solid support components thereof) used in the practice of the present disclosure are typically described in EP Barrett, LG Joyner, PP Halenda, J. Am. Chem. Soc. (1951) 73:373-380] and ASTM D4222-03 (2008) (method referred to herein as the "BJH method"), both expressly incorporated herein by reference in their entirety. and by a pore specific volume measurement method, also by a mercury porosimetry method (e.g., a mercury porosimetry such as Micromeritics Autopore V 9605 Mercury Porosimeter (Micromeritics Autopore V 9605 Mercury Porosimeter) (Micromeritics Autopore V 9605 Mercury Porosimeter, Norcross, GA) 0.1 cm ³ /g to 1.5 cm ³ /g or any number in between, 0.1 cm ³ /g to 0.8 cm, as measured by Micromeritics Instrument Corp. (using according to manufacturer's instructions) ³ /g or any number in between, 0.1 cm ³ /g to 0.7 cm ³ /g or any number in between, 0.1 cm ³ /g to 0.6 cm ³ /g or any number in between, 0.1 cm ³ /g to 0.5 cm ³ /g or any number in between, 0.2 cm ³ /g to 0.8 cm ³ /g or any number in between, 0.2 cm ³ /g to 0.7 cm ³ /g or any number therebetween any number between, 0.2 cm ³ /g to 0.6 cm ³ /g or any number in between, 0.2 cm ³ /g to 0.5 cm ³ /g or any number in between, 0.3 cm ³ /g to 1 cm ³ /g or any number in between, 0.3 cm ³ /g to 0.9 cm ³ /g or any number in between, 0.3 cm ³ /g to 0.8 cm ³ /g or any number in between , 0.3 cm ³ /g to 0.7 cm ³ /g or any number in between, 0.3 cm ³ /g to 0.6 cm ³ /g or any number in between, or 0.3 cm ³ /g to 0.5 cm ³ / g or any number in between, or a specific pore volume (measured based on pores having a diameter of 1.7 nm to 100 nm) within the range defined by any two values mentioned above. See, eg, ASTM 3663, ASTM D-4284-12 and D6761-07 (2012), all of which are expressly incorporated herein by reference in their entirety.

Typically, the heterogeneous oxidation catalyst has an average pore diameter in the range of 10 nm to 100 nm or any number in between, as measured by the BJH method and/or mercury porosimetry. More typically, the heterogeneous oxidation catalyst has an average pore diameter in the range of 10 nm to 90 nm, or any number in between, as measured by the BJH method and/or mercury porosimetry. In some embodiments, the average pore diameter, as measured by the BJH method and/or mercury porosimetry, ranges from 10 nm to 80 nm or any number therebetween, or ranges from 10 nm to 70 nm or any number therebetween. number, or in the range of 10 nm to 60 nm or any number in between, also often in the range of 10 nm to 50 nm or any number in between. In some embodiments, the average pore diameter, as measured by the BJH method and/or mercury porosimetry, ranges from 20 nm to 100 nm or any number in between. In these particular embodiments, the average pore diameter, as measured by the BJH method and/or mercury porosimetry, ranges from 20 nm to 90 nm or any number therebetween, or ranges from 20 nm to 80 nm or any number therebetween. , or in the range of 20 nm to 70 nm or any number in between, or in the range of 20 nm to 60 nm or any number in between, or in the range of 10 nm to 50 nm or any number in between. Catalysts used in the practice of the present disclosure typically have a relatively high concentration of pores in the size ranges described above.

Suitable heterogeneous oxidation catalysts are described by Renovia and Stora Enso in PCT Application No. PCT/US17/13197, expressly incorporated herein by reference in its entirety as previously mentioned.

In some embodiments, the heterogeneous oxidation catalyst may be prepared on an extruded support. Catalysts with extruded supports are beneficial for use in many industrial applications that can be used in the production of FDCA pathway products, such as continuous industrial fixed bed reactors. Industrial fixed bed reactors must utilize suitably shaped and sized catalysts, such as extrudates, to avoid the excessive pressure drop associated with the use of powdered catalysts, which are typically difficult to utilize industrially in fixed bed reactor systems.

In a further embodiment, the metal and/or accelerator may optionally be located in a shell covering the outer surface area of the extruded support, and thus the catalytically active surface as a metal that may be inaccessible to the reaction medium when disposed in the center of the support. and an accelerator to the reaction medium. In some embodiments, the outer surface area of the extruded support includes the surface area of the surface of the outer layer of the extruded support. In some embodiments, the external surface area of the extruded support includes the surface area of the pores of the extruded support.

In some embodiments, the extruded support comprises carbon, zirconium dioxide, titanium dioxide, silicon carbide, silicon dioxide, Al ₂ O ₃ , montmorillonite, or any combination thereof.

In carrying out the method of making an FDA pathway product, oxygen is provided in pure form (ie, O ₂ alone without other gases) or as a component of a mixture of gases (eg, air, oxygen-enriched air, etc.) It can be. The molar ratio of oxygen to furanic oxidizing substrate during the contacting step is typically in the range of 2:1 to 10:1. In some embodiments, the molar ratio of oxygen to furanic oxidizing substrate is from 2:1 to 10:1, or from 3:1 to 5:1. During the contacting step, oxygen is typically present at a partial pressure in the range of 50 psig to 1000 psig or any number in between. More typically, the oxygen is present at a partial pressure in the range of 50 psig to 200 psig or any number in between. In some embodiments, the oxygen is 50-200 psig, 100-300 psig, 200-400 psig, 300-500 psig, 400-600 psig, 500-700 psig, 600-800 psig, 700-900 psig, or 800- Partial pressures in the 1000 psig range or any number in between, or within the range defined by any two partial pressures mentioned above.

The contacting (oxidation) step is typically carried out at a temperature in the range of 50°C to 200°C or any number in between. In some embodiments, the contacting step is performed at a temperature ranging from 80 °C to 180 °C or any number in between, in other embodiments, the contacting step is performed at a temperature ranging from 90 °C to 160 °C or any number in between or 100 °C. at a temperature in the range of °C to 160 °C or any number in between. In certain preferred embodiments, the contacting step is conducted at a temperature in the range of 90 °C to 180 °C or any number in between, sometimes it is conducted at a temperature in the range of 110 °C to 160 °C or any number in between.

In some embodiments, it may be desirable to perform oxidation of a furanic oxidized substrate to a desired FDCA pathway product in a series of two or more oxidation steps, wherein a first oxidation step is as described above and a second oxidation step Is,

(b) a second oxidation feedstock comprising a second furanic oxidation substrate and a second oxidation solvent sufficient to form a second reaction mixture for oxidizing the second furanic oxidation substrate to produce a second FDCA pathway product; contacting with oxygen in the presence of a second heterogeneous oxidation catalyst under conditions

including,

(first) contacting step (a) produces a first FDCA pathway product, which is an FDCA pathway intermediate compound, alone or together with FDCA;

The second furanic oxidation substrate is a product of the first FDCA pathway;

the second reaction mixture is substantially free of added base;

the second heterogeneous oxidation catalyst comprises a second solid support and a noble metal which may be the same as or different from the (first) noble metal in step (a);

The second heterogeneous oxidation catalyst has a plurality of pores and a range of 20 m ² /g to 500 m ² /g or any number in between, such as 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500 m ² /g, or by any two surface areas mentioned above. It includes the specific surface area within the defined range.

The second FDCA pathway product is a downstream oxidation product of the first FDCA pathway product and typically includes FFCA, or FDCA. Typically, the second FDCA pathway product includes FDCA. Typically, the second oxidation step has no base added.

Suitable noble metals, catalytic metal loadings, solid support materials, and reaction conditions (e.g., reaction temperature, oxygen (partial) pressure, molar ratio of oxygen to furanic oxidizing substrate, etc.) suitable for use in the first oxidation process are also suitable for use in the second oxidation process. suitable for use in methods. The second heterogeneous oxidation catalyst may be the same as or different from the one used in the first oxidation process (ie, the “first heterogeneous oxidation catalyst”). Oxidation solvents suitable for use in the second oxidation feedstock are the same as those suitable for use in the first oxidation process (ie, "first oxidation solvent"). A multi-step oxidation process format may be desirable when optimal production of the desired FDCA pathway product requires a change in reaction conditions during the conversion of the furanic oxidized substrate to the desired FDCA pathway product. For example, the second oxidation reaction is conducted at a higher or lower temperature than the first oxidation reaction, or the molar ratio of oxygen to feedstock component in the second oxidation reaction is maintained at a higher or lower ratio than in the first oxidation reaction, or It may be desirable to maintain the partial pressure of oxygen in the second oxidation reaction at a higher or lower partial pressure than in the first oxidation reaction. The composition of the second oxidation solvent may be the same as the composition of the first oxidation solvent, or it may be different. If they are different, they may still have one or more of the same solvent species components in common. The noble metal in the second heterogeneous oxidation catalyst is typically platinum, gold, or a combination thereof. Typically, the noble metal used in the second heterogeneous oxidation catalyst is platinum.

The FDCA pathway product(s) produced by the oxidation methods described herein can be recovered from the reaction mixture by separating the heterogeneous oxidation catalyst from a product solution comprising the FDCA pathway product(s) and an oxidation solvent. The product solution includes the oxidation solvent and soluble components of the reaction mixture, excluding the heterogeneous oxidation catalyst. The product solution can be further concentrated with respect to soluble components by partial removal of the oxidizing solvent. Oxidative solvent removal may be accomplished by evaporation (eg, by use of an evaporator), distillation, and the like.

Alternatively, or in addition to the isolation step, the FDCA pathway product can be crystallized. Accordingly, in one embodiment, the present disclosure provides

providing a crystallization solution comprising a FDCA pathway product and a crystallization solvent that is a solvent selected from the group consisting of organic solvents and multi-component solvents; initiating crystallization of the FDCA pathway product; and generating a plurality of FDCA pathway product crystals of different particle sizes.

It provides a method for preparing a crystalline FDCA pathway product composition comprising a.

As used herein, the term “crystallization solvent” refers to the ability of an FDCA pathway product to dissolve when subjected to conditions that cause a decrease in solubility of the FDCA pathway product in the crystallization solvent (eg, reduction in temperature (cooling) or solvent removal). Refers to a solvent capable of crystallization. The crystallization solvent can be water, an organic solvent, or a multi-component solvent comprising water and a water-miscible organic solvent or two or more organic solvent species. The crystallization process may follow a direct oxidation process (eg, a single-stage oxidation process or a multi-stage oxidation process), or it may follow other unit operations downstream of the oxidation process.

When crystallization is followed by FDCA pathway product production, the crystallization solution is typically a product solution comprising an FDCA pathway product and an oxidizing solvent. Thus, in this embodiment, the crystallization solvent is the same as the oxidation solvent (eg, the first oxidation solvent (single stage oxidation) or the second oxidation solvent (two-stage oxidation)). Some solvents suitable for use in the oxidation solvent are also suitable for use as the crystallization solvent.

Industrial solution phase crystallization is typically carried out by introducing a saturated (or supersaturated) solution of the product into a crystallizer where the solution is subjected to crystallization conditions, and crystallization is accomplished by, for example, reducing the temperature or solvent evaporation (e.g. e.g., solvent removal), or a combination of the two. Solvent evaporation can be used to concentrate the solution to initiate crystallization, and can also be used to adjust the solvent composition to reduce the solubility of the FDCA pathway product. As used herein, the term “crystallization conditions” refers to the adjustment of the temperature and/or the adjustment of the crystallization solution concentration and/or the adjustment of the crystallization solution composition that causes the initiation of crystallization of the FDCA pathway product.

In one embodiment, when the crystallization conditions include temperature adjustment, the present disclosure

ranges from 50°C to 220°C or any number in between, such as 50, 60, 70, 80, 90, 100, 110, 115, 120, 130, 140, 150, 160, 180, 190, 200, 210, or providing a crystallization solution comprising an FDCA pathway product and a crystallization solvent at a first temperature of 220° C. or within a range defined by any two temperatures noted above; and

cooling the crystallization solution to a second temperature lower than the first temperature to form a plurality of FDCA pathway product crystals of different particle sizes.

It provides a method for preparing a crystalline FDCA preparation comprising a.

Cooling reduces the solubility of the FDCA pathway product in the crystallization solvent, allowing crystals of the FDCA pathway product to form in solution. The first temperature typically ranges from 60° C. to 180° C. or any number in between, such as for example 60, 70, 80, 90, 100, 110, 115, 120, 130, 140, 150, 160, or 180 °C, or within the range defined by any two temperatures mentioned above. In some embodiments, the first temperature ranges from 70°C to 150°C or any number in between, such as 70, 80, 90, 100, 110, 115, 120, 130, 140, or 150°C, or as noted above. within the range defined by any two temperatures. When the crystallization solution is cooled, it is typically at or below 60°C, such as for example up to 60, 50, 40, 30, 20, 10, 5, or 0°C, or by any two temperatures mentioned above. It is cooled to a temperature within a defined range. More typically, it is defined by a temperature of less than or equal to 50°C or less than or equal to 40°C, such as for example less than or equal to 50, 40, 30, 20, 10, 5, or 0°C, or any two of the above mentioned temperatures. cooled to a temperature within the range

Suitable crystallization techniques are described by Renovia and Stora Enso in PCT Application No. PCT/US17/13197, expressly incorporated herein by reference in its entirety as previously mentioned.

The crystallization methods of the present disclosure can be performed using known industrial crystallizer systems suitable for performing solution phase crystallization. Suitable systems include, for example, batch crystallizers, continuous crystallizers (eg, forced circulation crystallizers, draft-tube crystallizers, draft-tube-baffle crystallizers, or Oslo-type crystallizers). etc.), and other such crystallizer systems.

Typically, the crystalline FDCA preparation comprises at least 98% by weight FDCA, more typically it comprises at least 99% by weight FDCA, and in some embodiments it comprises greater than 99% by weight FDCA.

II. Route to produce purified FDCA pathway products

Comprising FDCA and 5-formylfurancarboxylic acid (FFCA) under conditions sufficient to form a reaction mixture for the reduction of FFCA to hydroxymethylfurancarboxylic acid (HMFCA) in the presence of a heterogeneous reduction catalyst and a solvent. A method of making a purified FDCA pathway product is described herein, which may involve contacting the FDCA pathway product with hydrogen and generating a purified FDCA pathway product. As used herein, the terms “purified furandicarboxylic acid pathway product” and “purified FDCA pathway product” refer to FDCA and FFCA in the presence of a heterogeneous reduction catalyst and a solvent to form a reaction mixture that reduces FFCA to HMFCA. are used interchangeably to refer to a product of a process wherein the FDCA pathway product comprising is contacted with hydrogen. A purified FDCA pathway product includes at least FDCA and HMFCA. In some embodiments, the methods of making purified FDCA pathway products described herein provide beneficial and advantageously high selectivity for the reduction of FFCA to HMFCA compared to the undesirable reduction of FDCA. In some embodiments, the methods of making purified FDCA pathway products described herein can be performed at relatively low temperatures, which can aid in the selective reduction of FFCA to HMFCA.

In some embodiments, the FDCA pathway product used in the method of making a purified FDCA pathway product can be the same FDCA pathway product prepared by the method described in Section I of this application. In some embodiments, the FDCA pathway products are FDCA, FFCA, and diformylfuran (DFF), hydroxymethylfurancarboxylic acid (HMFCA), 5-(hydroxymethyl)furfural (HMF), tetrahydrofuran dica carboxylic acid (THFDCA), and/or 5-methyl-2-furoic acid (MFA), or any combination thereof. In some embodiments, the FDCA pathway product comprises FDCA, FFCA, and one or more additional FDCA pathway intermediate compounds selected from diformylfuran (DFF) and/or hydroxymethylfurancarboxylic acid (HMFCA) or mixtures thereof can do. In some embodiments, the FDCA pathway product is FDCA, FFCA, and 5-(hydroxymethyl)furfural (HMF), tetrahydrofuran dicarboxylic acid (THFDCA), and/or 5-methyl-2-furoic acid ( MFA), or any combination thereof.

The heterogeneous reduction catalyst used in the process for preparing the purified FDCA pathway product may include a metal dispersed on the surface of a solid support. In some embodiments, the metal can be selected from cobalt, nickel, copper, silver, gold, ruthenium, rhodium, palladium, osmium, iridium and/or platinum, or combinations thereof. In some embodiments, the metal is selected from the group consisting of nickel, ruthenium, copper, silver, gold, platinum and iridium, or combinations thereof. In some embodiments, the metal is nickel. In some embodiments, the metal is ruthenium. In some embodiments, the metal is platinum. The heterogeneous reduction catalyst may further include a promoter for enhancing the performance of the heterogeneous reduction catalyst. Suitable promoters may include Ti, Zr, Cr, Mo, W, Mn, Ru, Cu, Zn, Sb, Bi, Sn, Au, Ag, Pb or Te. When the metal is platinum or gold, or combinations thereof, suitable accelerators include, for example, Bi, Te, Sn, Pd, Ir, Mo and/or W. In some embodiments, the accelerator is Bi. In some embodiments, the accelerator is Te. In some embodiments, the accelerator is Sn.

In some embodiments, the solid support comprises carbon, zirconium dioxide, silicon carbide, silicon dioxide, Al ₂ O ₃ , or any combination thereof. In some embodiments, the support comprises carbon. In some embodiments, the solid support comprises carbon having a surface area of less than (but not zero) 200 m ² /g. In some embodiments, the solid support comprises the shaped porous carbon support described by Rennovia in Diamond et al., WO 2017/075391 and Sokolovsky et al. All of which are expressly incorporated herein.

In some embodiments, the heterogeneous reduction catalyst can be Cu/SiO ₂ , Cu/Mn/Al ₂ O ₃ , Ni/Al ₂ O ₃ , Pd/C, Pt/C, or Ru/C. In some embodiments, the heterogeneous reduction catalyst can be obtained from commercial sources as a commercially available product, such as, but not limited to, BASF Cu 0602, Clariant Cu T-4874, Johnson Matthey (JM) Ni HTC 500 RP, JM- 4 Pd/C, JM-6 Pd/C, JM-10 Pd/C, JM-24 Pt/C, JM-27 Pt/C, JM-37 Ru/C, or JM-38 Ru/C.

In some embodiments, the heterogeneous reduction catalyst may be made into a powder. In some embodiments, the heterogeneous reduction catalyst is reduced by applying it to a forming gas. In some embodiments, the heterogeneous reduction catalyst heats it to an elevated temperature (e.g., 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, or greater than 400°C) in a forming gas for several hours (e.g., eg, for 2, 3, 4, or longer).

The heterogeneous reduction catalyst may include metal loaded on a solid support in the range of 0.3% to 5% by weight of the total catalyst, or any number in between. In some embodiments, the metal loading is 0.5% to 4%, 2% to 7%, 4% to 10%, 6% to 12%, 8% to 15%, 10% % to 20%, 15% to 25%, 20% to 40%, 30% to 50%, or 40% to 60% or 50% to 70% by weight or in the range of these is any number between In some embodiments, the metal loading is in the range of 2-4 weight percent or any number in between. In some embodiments, the metal loading is 2% by weight. In some embodiments, the metal loading is 3% by weight. In some embodiments, the metal loading is 4% by weight. In some embodiments, the metal loading is in the range of 20-70% by weight or any number in between. In some embodiments, the metal loading is 20% by weight. In some embodiments, the metal loading is 30% by weight. In some embodiments, the metal loading is 40% by weight. In some embodiments, the metal loading is 50% by weight. In some embodiments, the metal loading is 60% by weight. In some embodiments, the metal loading is 70% by weight. When two or more metals are used, the heterogeneous reduction catalyst may comprise a plurality of heterogeneous reduction catalyst particles each comprising two or more metals, or the heterogeneous reduction catalyst may comprise a plurality of heterogeneous reduction catalyst metal-particle species. A mixture, eg, a first plurality of heterogeneous reduction catalyst particles comprising a first metal species and a second plurality of heterogeneous reduction catalyst particles comprising a second metal species.

The solid support component of the heterogeneous reduction catalyst may include any type of material suitable for use as a catalyst support. Suitable materials include, for example, metal oxides, carbonaceous materials, polymers, metal silicates, and/or metal carbides, or any composite material made therefrom. In some embodiments, the metal oxide includes silicon oxide (silica), zirconium oxide (zirconia), titanium oxide (titania), titanium dioxide, and/or aluminum oxide (alumina). As used herein, the term "carbonaceous" refers to graphite and carbon black, which may or may not be in activated form. In some embodiments, metal silicates include, for example, orthosilicates, borosilicates, or aluminosilicates (eg, zeolites). In some embodiments, the metal carbide includes, for example, silicon carbide and the like. In some embodiments, the polymeric solid support material comprises polystyrene, polystyrene-co-divinyl benzene, polyamide, or polyacrylamide.

Suitable solid support materials include composite materials made from or comprising a binder and a material selected from metal oxides, carbonaceous materials, polymers, metal silicates, and/or metal carbides or mixtures thereof. In some embodiments, the binder is a resin. In some embodiments, the composite material includes a carbonized binder and a material selected from the group consisting of metal oxides, carbonaceous materials, metal silicates, and metal carbides. In one embodiment, the composite material includes a carbonized binder and carbon black, which may or may not be in activated form.

In some embodiments, the solid support is Aditya Birla CDX-KU, Aditya Birla CSCUB, Aditya Birla R2000B, Aditya Birla R2500UB, Aditya Birla R3500B, Aditya Birla R3500B Tiya Birla R5000U2, Arosperse 5-183A, Asbury 5302, Asbury 5303, Asbury 5345, Asbury 5348R, Asbury 5358R, Asbury 5365R, Asbury 5368, Asbury 5375R, Asbury 5379, Asbury A99, Cabot Monarch 120, Cabot Monarch 280, Cabot Monarch 570, Cabot Monarch 700, Cabot Norit Darco 12x20L1, Cabot Vulcan Vulcan XC72, Continental N120, Continental N234, Continental N330, Continental N330-C, Continental N550, Norit ROX 0.8, Orion Arosperse 138, Orion Arosperse 15, Orion Color Black ( Orion Color Black) FW 2, Orion Color Black FW 255, Orion HiBlack 40B2, Orion Hi-Black 50 L, Orion Hi-Black 50 LB, Orion Hi-Black 600 L, Orion HP-160, Orion Lamp Orion Lamp Black 101, Orion N330, Orion Printex L6, Sid Richardson Ground N115, Sid Richardson Ground SR155, Sid Richardson SC159, Sid Richardson SC419, Timkal Ensaco (Timcal Ensaco) 150G, Timcal Ensaco 250G, Timcal Ensaco 260G, and/or Timcal Ensaco 350G or any combination thereof.

Metal impregnation of the solid support typically causes negligible changes in the specific surface area, pore diameter, and specific volume of the solid support. Heterogeneous reduction catalysts suitable for use in the present disclosure typically have a plurality of pores and eg in the range of 20 m ² /g to 500 m ² /g, such as 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500 m ² /g, or any of the aforementioned It is prepared using a solid support having a specific surface area within the range defined by the two surface areas. The specific surface area is measured using known methods such as Brunauer, Emmett and Teller (J. Am. Chem. Soc. 1938, 60:309-311) and/or mercury porosimetry It can be. See, eg, ASTM test methods D3663, D6556, and D4567, each of which is expressly incorporated herein by reference in its entirety. In some embodiments, the heterogeneous reduction catalyst (or solid support) used in the process for making the purified FDCA pathway product has a range of 25 m ² /g to 250 m ² /g or any number in between, and sometimes 25 m 2 /g. m ² /g to 225 m ² /g or any number in between, or 25 m ² /g to 200 m ² /g or any number in between, or 25 m ² /g to 175 m ² /g range or any number in between, or between 25 m ² /g and 150 m ² /g or any number in between, or between 25 m ² /g and 125 m ² /g or any number in between , or a specific surface area ranging from 25 m ² /g to 100 m ² /g or any number in between.

Heterogeneous reduction catalysts (and solid support components thereof) used in the practice of this disclosure are described in EP Barrett, LG Joyner, PP Halenda, J. Am. Chem. Soc. (1951) 73:373-380] and ASTM D4222-03 (2008) (method referred to herein as the "BJH method"), both expressly incorporated herein by reference in their entirety. and by a pore specific volume measurement method, also by a mercury porosimetry method (e.g., a mercury porosimetry such as Micromeritics Autopore V 9605 Mercury Porosimeter (Micromeritics Autopore V 9605 Mercury Porosimeter) (Micromeritics Autopore V 9605 Mercury Porosimeter, Norcross, GA) 0.1 cm ³ /g to 1.5 cm ³ /g or any number in between, 0.1 cm ³ /g to 0.8 cm, as measured by Micromeritics Instrument Corp. (using according to manufacturer's instructions) ³ /g or any number in between, 0.1 cm ³ /g to 0.7 cm ³ /g or any number in between, 0.1 cm ³ /g to 0.6 cm ³ /g or any number in between, 0.1 cm ³ /g to 0.5 cm ³ /g or any number in between, 0.2 cm ³ /g to 0.8 cm ³ /g or any number in between, 0.2 cm ³ /g to 0.7 cm ³ /g or any number therebetween any number between, 0.2 cm ³ /g to 0.6 cm ³ /g or any number in between, 0.2 cm ³ /g to 0.5 cm ³ /g or any number in between, 0.3 cm ³ /g to 1 cm ³ /g or any number in between, 0.3 cm ³ /g to 0.9 cm ³ /g or any number in between, 0.3 cm ³ /g to 0.8 cm ³ /g or any number in between , 0.3 cm ³ /g to 0.7 cm ³ /g or any number in between, 0.3 cm ³ /g to 0.6 cm ³ /g or any number in between, or 0.3 cm ³ /g to 0.5 cm ³ / g or any number in between, or a specific pore volume (measured based on pores having a diameter of 1.7 nm to 100 nm) within the range defined by any two values mentioned above. See, eg, ASTM 3663, ASTM D-4284-12 and D6761-07 (2012), all of which are expressly incorporated herein by reference in their entirety.

Typically, the heterogeneous reduction catalyst has an average pore diameter in the range of 10 nm to 100 nm or any number in between, as measured by the BJH method and/or mercury porosimetry. In some embodiments, the heterogeneous reduction catalyst has an average pore diameter in the range of 10 nm to 90 nm, or any number in between, as measured by the BJH method and/or mercury porosimetry. In some embodiments, the average pore diameter, as measured by the BJH method and/or mercury porosimetry, ranges from 10 nm to 80 nm or any number therebetween, or ranges from 10 nm to 70 nm or any number therebetween. number, or in the range of 10 nm to 60 nm or any number in between, also often in the range of 10 nm to 50 nm or any number in between. In some embodiments, the average pore diameter, as measured by the BJH method and/or mercury porosimetry, ranges from 20 nm to 100 nm or any number in between. In these particular embodiments, the average pore diameter, as measured by the BJH method and/or mercury porosimetry, ranges from 20 nm to 90 nm or any number therebetween, or ranges from 20 nm to 80 nm or any number therebetween. , or in the range of 20 nm to 70 nm or any number in between, or in the range of 20 nm to 60 nm or any number in between, or in the range of 10 nm to 50 nm or any number in between.

In some embodiments, the heterogeneous reduction catalyst may be prepared on an extruded support. Catalysts with extruded supports are beneficial for use in many industrial applications that can be used in the production of purified FDCA pathway products, such as continuous industrial fixed bed reactors. Industrial fixed bed reactors must utilize suitably shaped and sized catalysts, such as extrudates, to avoid the excessive pressure drop associated with the use of powdered catalysts, which are typically difficult to utilize industrially in fixed bed reactor systems.

In a further embodiment, the metal and/or accelerator may optionally be located in a shell covering the outer surface area of the extruded support, and thus the catalytically active surface as a metal that may be inaccessible to the reaction medium when disposed in the center of the support. and an accelerator to the reaction medium. In some embodiments, the outer surface area of the extruded support includes the surface area of the surface of the outer layer of the extruded support. In some embodiments, the external surface area of the extruded support includes the surface area of the pores of the extruded support.

In some embodiments, the extruded support comprises carbon, zirconium dioxide, titanium dioxide, silicon carbide, silicon dioxide, Al ₂ O ₃ , montmorillonite, or any combination thereof.

In some embodiments, the solvent used in the process of making a purified FDCA pathway product is an aprotic organic solvent (e.g., an ether, ester, and/or ketone, or mixture thereof) alone (e.g., , as a single-component solvent) or as a component of a multi-component solvent. When used in a multi-component solvent, the aprotic organic solvent is typically miscible with the other component(s) of the multi-component solvent. In some embodiments, multi-component solvents can include water and water-miscible organic solvents. Typically, the water-miscible organic solvent is a water-miscible aprotic organic solvent.

Candidate component solvents for multi-component solvents are not limited to FDCA pathway products and solvents in which the purified FDCA pathway products are highly soluble. Multi-component solvents can exhibit a synergistic solvation effect on FDCA even when FDCA is sparingly soluble in each component solvent. For example, FDCA has poor solubility in water. When paired with a water-miscible organic solvent with poor FDCA-solvation ability, the combination of water and water-miscible organic solvent can exhibit enhanced FDCA-solvation ability. Additionally, in some embodiments, the multi-component solvents disclosed herein are beneficial and advantageous because the multi-component solvents exhibit enhanced FDCA-solvation capabilities. In some embodiments, the multi-component solvents disclosed herein are advantageous because the same solvents can be used to make FDCA pathway products and purified FDCA pathway products. In some embodiments, the methods for preparing purified FDCA pathway products described herein are beneficial and advantageously provide high selectivity for reducing FFCA to HMFCA compared to reduction of undesirable FDCA. In some embodiments, the methods of making purified FDCA pathway products described herein can be performed at relatively low temperatures, which can aid in the selective reduction of FFCA to HMFCA.

Exemplary multi-component solvents that exhibit this effect include those comprising water and water-miscible aprotic organic solvents. Exemplary water-miscible aprotic solvents suitable for use in the practice of the present disclosure include tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2- pyrrolidone ("NMP"), methyl ethyl ketone ("MEK"), and/or gamma-valerolactone or mixtures thereof. Preferably, the water miscible aprotic organic solvent is an ether such as, for example, glyme, dioxane (1,4-dioxane), dioxolane (eg 1,3-dioxolane), and/or tetrahydrofuran, or mixtures thereof. Glymes suitable for use in the practice of the present disclosure include, for example, monoglyme (1,2-dimethoxyethane, “DME”), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, tri glyme, butyl diglyme, tetraglyme, polyglyme, and/or highly ethoxylated diethers of high molecular weight alcohols (“hyglyme”) or mixtures thereof. Often, the organic solvent is a multi-component solvent comprising water and a water-miscible aprotic organic solvent that is glyme, diglyme or dioxane or mixtures thereof.

In some embodiments, the multi-component solvent includes water and dioxane. In some embodiments, the multi-component solvent includes water and DME. In some embodiments, the multi-component solvent includes water and diglyme. In some embodiments, the multi-component solvent includes water and triglyme. In some embodiments, the multi-component solvent includes water and tetraglyme. In some embodiments, the multi-component solvent includes water and hyglyme. In some embodiments, the multi-component solvent includes water and NMP. In some embodiments, the multi-component solvent includes water and MEK. In some embodiments, the multi-component solvent includes water and gamma-valerolactone.

In some embodiments, the composition of the oxidation solvent used to make the purified FDCA pathway product is determined by a downstream process (e.g., to facilitate product recovery, further purification, etc.), or an upstream process (e.g., FDCA It may be the same as the solvent used for the route product process). In some embodiments, it may be desirable to use organic solvents that are multi-component solvents that include light solvents and heavy solvents. When the multi-component solvent includes water and a water-miscible organic solvent, the water-miscible organic solvent may be a light water-miscible organic solvent (eg, a water-miscible organic solvent having a boiling point occurring at a temperature lower than that of water), or It may be a heavy water-miscible organic solvent (eg, a water-miscible organic solvent having a boiling point occurring at a temperature higher than the boiling point of water). Typically, the light and heavy water-miscible organic solvents are light and heavy aprotic organic solvents, respectively. Exemplary light water-miscible (and aprotic) organic solvents used with water in multi-component solvents include, for example, glyme, dioxolane (eg, 1,3-dioxolane), and/or tetrahydro Furan; etc. are included. Exemplary heavy water-miscible (and aprotic) organic solvents used with water in multi-component solvents include, for example, dioxane, ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme , butyl diglyme, tetraglyme, and/or polyglyme. In some embodiments (eg, continuous reactor systems), all or a portion of the organic solvent or components thereof may be removed from the product solution (eg, by distillation) and recycled to the reaction mixture. In such an embodiment, a composition corresponding to or capable of forming an azeotrope at the temperature used during the reduction step (eg, the contacting step), or at the temperature used during the process upstream or downstream of the reduction step ( For example, it may be desirable to use a multi-component solvent having an "azeotropic composition"). The use of such a multi-component solvent with an azeotrope composition can facilitate recycling of the organic solvent (as part of the azeotrope composition) to the reduction step, or to processes occurring upstream and/or downstream of the reduction step.

In some embodiments, the water-miscible organic solvent species comprises at least 5 vol %, at least 10 vol %, at least 15 vol %, at least 20 vol %, at least 25 vol %, at least 30 vol %, at least 35 vol%, at least 40 vol%, at least 45 vol%, at least 50 vol%, at least 55 vol%, at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, at least 80 vol%, at least 85 vol%, at least 90 vol%, or at least 95 vol%; Correspondingly, water typically represents less than 95 vol%, less than 90 vol%, less than 85 vol%, less than 80 vol%, less than 75 vol%, less than 70 vol%, less than 65 vol%, 60 vol% of the multicomponent system, respectively. Less than 55 vol%, Less than 50 vol%, Less than 45 vol%, Less than 40 vol%, Less than 35 vol%, Less than 30 vol%, Less than 25 vol%, Less than 20 vol%, Less than 15 vol%, 10 vol% less than, or less than 5 vol % or within the range defined by any two volume % mentioned above.

In some embodiments, the multi-component solvent comprises water in the range of 1-5% by weight or any number in between and water miscible organic solvent in the range of 99-95% by weight or any number in between. In some embodiments, the multi-component solvent comprises water in the range of 5-10% by weight or any number in between and water miscible organic solvent in the range of 5-10% by weight or any number in between. In some embodiments, the multi-component solvent comprises water in the range of 10-15% by weight or any number therebetween and water miscible organic solvent in the range of 90-85% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 15-20% by weight or any number therebetween and water miscible organic solvent in the range of 85-80% by weight or any number in between. In some embodiments, the multi-component solvent comprises water in the range of 20-25% by weight or any number therebetween and water miscible organic solvent in the range of 80-75% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 25-30% by weight or any number therebetween and water miscible organic solvent in the range of 75-70% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 30-35% by weight or any number therebetween and water miscible organic solvent in the range of 70-65% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 35-40% by weight or any number therebetween and water miscible organic solvent in the range of 65-60% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 40-45% by weight or any number therebetween and water miscible organic solvent in the range of 60-55% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 45-50% by weight or any number therebetween and water miscible organic solvent in the range of 65-50% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 50-55% by weight or any number therebetween and water miscible organic solvent in the range of 50-45% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 55-60% by weight or any number therebetween and water miscible organic solvent in the range of 45-40% by weight or any number in between. In some embodiments, the multi-component solvent comprises water in the range of 60-65% by weight or any number therebetween and water miscible organic solvent in the range of 40-35% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 65-70% by weight or any number therebetween and water miscible organic solvent in the range of 35-30% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 70-75% by weight or any number therebetween and water miscible organic solvent in the range of 30-25% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 75-80% by weight or any number therebetween and water miscible organic solvent in the range of 25-20% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 80-85% by weight or any number therebetween and water miscible organic solvent in the range of 20-15% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 85-90% by weight or any number therebetween and water miscible organic solvent in the range of 15-10% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 90-95% by weight or any number therebetween and water miscible organic solvent in the range of 10-5% by weight or any number therebetween. In some embodiments, the multi-component solvent comprises water in the range of 95-99% by weight or any number therebetween and water miscible organic solvent in the range of 5-1% by weight or any number therebetween.

In some embodiments, the volume ratio of water to water-miscible organic solvent ranges from 1:6 to 6:1 or any number in between. In certain embodiments, the volume ratio ranges from 1:4 to 4:1, or any number of water:water-miscible organic solvents in between. In some embodiments, the volume ratio ranges from 1:4 to 3:1, or any number of water:water-miscible organic solvents in between. In some embodiments, the volume ratio is in the range of 1:3 to 3:1, or any number of water:water miscible organic solvents in between. In certain embodiments, the volume ratio is 1:1 water:water miscible organic solvent. In some embodiments, the volume ratio is 3:2 water:water miscible organic solvent.

In some embodiments, the weight percent ratio of water to water miscible organic solvent ranges from 1:6 to 6:1 or any number in between. In certain embodiments, the weight percent ratio is in the range from 1:4 to 4:1, or any number of water:water-miscible organic solvents in between. In some embodiments, the weight percent ratio ranges from 1:4 to 3:1, or any number in between, water:water miscible organic solvent. In some embodiments, the weight percent ratio is in the range of 1:3 to 3:1, or any number of water:water miscible organic solvents in between. In certain embodiments, the weight percent ratio is 1:1 water:water miscible organic solvent. In some embodiments, the weight percent ratio is 3:2 water:water miscible organic solvent.

In some embodiments, the multi-component solvent includes water and two different water-miscible organic solvents. Typically both water-miscible organic solvents are water-miscible aprotic organic solvents. The two water-miscible aprotic solvents are each independently tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone ("NMP "), methyl ethyl ketone ("MEK"), and/or gamma-valerolactone. One or both of the water-miscible aprotic organic solvents may be ethers such as, for example, glyme, dioxane (eg 1,4-dioxane), dioxolane (eg 1,3-dioxane) solan), tetrahydrofuran, and the like. Glyme is, for example, monoglyme (1,2-dimethoxyethane, “DME”), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglyme, and/or highly ethoxylated diethers of high molecular weight alcohols ("hyglymes").

In some embodiments, the volume ratio of water to the first and second water-miscible organic solvents is approximately 1:1:1 (v:v:v). In some embodiments, the volume ratio of water to the first and second water-miscible organic solvents is approximately 1:2:1 (v:v:v). In some embodiments, the volume ratio of water to the first and second water-miscible organic solvents is approximately 1:2:2 (v:v:v). In some embodiments, the volume ratio of water to the first and second water-miscible organic solvents is approximately 2:1:1 (v:v:v).

In some embodiments, the amount of water included in the multi-component solvent is, for example, at least 0.01 M, at least 0.02 M, at least 0.05 M, at least 0.10 M, at least 0.15 M, at least 0.25 M, at least 0.30 M, at least 0.35 M, at least or It may be within the range defined by any two concentrations mentioned above. In some embodiments, the concentration of water in the multi-component solvent is in the range of 0.01-3.0 M, 0.05-2.0 M, 0.10-1.0 M, or 0.20-0.50 M, or any concentration within the aforementioned ranges. Water may be present in a concentration of at least 0.20 M in the multi-component solvent. Water is present in the multi-component solvent at, for example, at least 0.2 M, or at least 0.3 M, or at least 0.4 M, or at least 0.5 M, or at least 0.6 M, or at least 0.8 M, or at least 1.0 M, or at least 1.25 M, or It may be present at a concentration of at least 1.5 M, or within the range defined by any two concentrations noted above. In some embodiments, water is present in the multi-component solvent at a concentration ranging from 0.2-2.0 M, 0.3-1.5 M, 0.4-1.25 M, 0.5-1.25 M, or 0.6-1.0 M, or any concentration within the aforementioned ranges. can

In some embodiments, the FDCA pathway product can be present in any concentration below its solubility limit in the reaction mixture. In some embodiments, the concentration of the FDCA pathway product in the reaction mixture is, for example, at least 0.01 M, at least 0.02 M, at least 0.05 M, at least 0.10 M, at least 0.15 M, at least 0.25 M, at least 0.30 M, at least 0.35 M, at least 0.40 M, at least 0.45 M, at least 0.50 M, at least 0.60 M, at least 0.70 M, at least 0.80 M, at least 0.90 M, at least 1.0 M, at least 1.5 M, at least 2.0 M, at least 2.5 M, or at least 3.0 M, or the above within the range defined by any two concentrations recited. In some embodiments, the concentration of the FDCA pathway product in the reaction mixture is in the range of 0.01-3.0 M, 0.05-2.0 M, 0.10-1.0 M, or 0.20-0.50 M, or any concentration within the aforementioned ranges. The FDCA pathway product may be present in the reaction mixture at a concentration of, for example, at least 0.20 M. The FDCA pathway product is present in the reaction mixture at least 0.2 M, at least 0.3 M, or at least 0.4 M, or at least 0.5 M, or at least 0.6 M, or at least 0.8 M, or at least 1.0 M, or at least 1.25 M, or at least 1.5 M, or at a concentration within the range defined by any two of the above-mentioned concentrations. In some embodiments, the FDCA pathway product is at a concentration in the reaction mixture ranging from 0.2-2.0 M, 0.3-1.5 M, 0.4-1.25 M, 0.5-1.25 M, or 0.6-1.0 M, or any within the aforementioned ranges. concentration can be present.

A method of making a purified FDCA pathway product can include conducting the process using a reaction mixture wherein the components of the reaction mixture are present in specified concentrations or ratios between the components. In some embodiments, the heterogeneous reduction catalyst and FDCA pathway product are present in a weight percent ratio of heterogeneous reduction catalyst:FDCA pathway product of 1:0.04 in the reaction mixture. In some embodiments, the heterogeneous reduction catalyst and FDCA pathway product are present in a weight percent ratio of heterogeneous reduction catalyst:FDCA pathway product of 1:0.12 in the reaction mixture. In some embodiments, the heterogeneous reduction catalyst and FDCA pathway product are present in a weight percent ratio of heterogeneous reduction catalyst:FDCA pathway product of 1:0.3 in the reaction mixture. In some embodiments, the heterogeneous reduction catalyst and FDCA pathway product are present in a weight percent ratio of heterogeneous reduction catalyst:FDCA pathway product of 1:0.5 in the reaction mixture. In some embodiments, the heterogeneous reduction catalyst and the FDCA pathway product are present in a 1:1 weight percent heterogeneous reduction catalyst:FDCA pathway product ratio in the reaction mixture.

In some embodiments, the heterogeneous reduction catalyst and the FDCA pathway product are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FDCA pathway product from 1:0.04 to 1:1, or any ratio between the aforementioned ranges. . In some embodiments, the heterogeneous reduction catalyst and the FDCA pathway product are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FDCA pathway product from 1:0.12 to 1:0.5, or any ratio between the aforementioned ranges. . In some embodiments, the heterogeneous reduction catalyst and the FDCA pathway product are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FDCA pathway product from 1:0.04 to 1:0.3, or any ratio between the aforementioned ranges. . In some embodiments, the heterogeneous reduction catalyst and the FDCA pathway product are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FDCA pathway product from 1:0.3 to 1:1, or any ratio between the aforementioned ranges. . In some embodiments, the heterogeneous reduction catalyst and the FDCA pathway product are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FDCA pathway product from 1:12 to 1:0.3, or any ratio between the aforementioned ranges. .

In some embodiments, the heterogeneous reduction catalyst and FFCA are present in a weight percent ratio of heterogeneous reduction catalyst:FFCA of 1:0.001 in the reaction mixture. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in a weight percent ratio of heterogeneous reduction catalyst:FFCA of 1:0.04 in the reaction mixture. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in a weight percent ratio of heterogeneous reduction catalyst:FFCA of 1:0.12 in the reaction mixture. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in a weight percent ratio of heterogeneous reduction catalyst:FFCA of 1:0.3 in the reaction mixture. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in a weight percent ratio of heterogeneous reduction catalyst:FFCA of 1:0.5 in the reaction mixture. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in a weight percent ratio of heterogeneous reduction catalyst:FFCA of 1:1 in the reaction mixture.

In some embodiments, the heterogeneous reduction catalyst and FFCA are present in the reaction mixture in a weight percent heterogeneous reduction catalyst:FFCA ratio of from 1:0.001 to 1:1, or any ratio between the aforementioned ranges. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in the reaction mixture in a weight percent heterogeneous reduction catalyst:FFCA ratio of from 1:0.04 to 1:1, or any ratio between the aforementioned ranges. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FFCA from 1:0.001 to 1:0.04, or any ratio between the aforementioned ranges. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FFCA from 1:0.12 to 1:0.5, or any ratio between the aforementioned ranges. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FFCA from 1:0.04 to 1:0.3, or any ratio between the aforementioned ranges. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FFCA from 1:0.3 to 1:1, or any ratio between the aforementioned ranges. In some embodiments, the heterogeneous reduction catalyst and FFCA are present in the reaction mixture in a weight percent ratio of heterogeneous reduction catalyst:FFCA from 1:12 to 1:0.3, or any ratio between the aforementioned ranges.

A method of making a purified FDCA pathway product may include performing the method at a specified temperature. In some embodiments, the method is performed at a temperature greater than 50 °C. In some embodiments, the method is performed at a temperature greater than 70 °C. In some embodiments, the method is performed at a temperature greater than 80 °C. In some embodiments, the method is performed at a temperature greater than 120 °C. In some embodiments, the method is performed at a temperature greater than 125 °C. In some embodiments, the method is performed at a temperature greater than 130 °C. In some embodiments, the method is performed at a temperature greater than 150 °C.

In some embodiments, the method of making a purified FDCA pathway product is performed at a temperature of 50°C. In some embodiments, the method is performed at a temperature of 70°C. In some embodiments, the method is performed at a temperature of 80°C. In some embodiments, the method is performed at a temperature of 120°C. In some embodiments, the method is performed at a temperature of 125°C. In some embodiments, the method is performed at a temperature of 130°C. In some embodiments, the method is performed at a temperature of 150°C.

In some embodiments, the method of making a purified FDCA pathway product is performed at a temperature of less than (but not zero) 50°C. In some embodiments, the method is performed at a temperature of less than (but not zero) 70°C. In some embodiments, the method is performed at a temperature of less than (but not zero) 80 °C. In some embodiments, the method is performed at a temperature of less than (but not zero) 120°C. In some embodiments, the method is performed at a temperature of less than (but not zero) 125°C. In some embodiments, the method is performed at a temperature of less than (but not zero) 130 °C. In some embodiments, the method is performed at a temperature of less than (but not zero) 150 °C.

In some embodiments of the present disclosure, the method of making a purified FDCA pathway product is performed at a temperature between 50°C and 130°C, or any number in between the aforementioned ranges. In some embodiments, the method is performed at a temperature between 80° C. and 120° C., or any number in between the aforementioned ranges. In some embodiments, the method is performed at a temperature between 70° C. and 125° C., or any number in between the aforementioned ranges. In some embodiments, the method is performed at a temperature between 50°C and 120°C, or any number in between the aforementioned ranges. In some embodiments, the method is performed at a temperature of 120° C. to 130° C., or any number in between the aforementioned ranges. In some embodiments, the method is performed at a temperature between 80° C. and 125° C., or any number in between the aforementioned ranges. In some embodiments, the method is performed at a temperature between 50°C and 150°C, or any number in between the aforementioned ranges.

A method of preparing a purified FDCA pathway product may include performing an ice process at a specified pressure. In some embodiments, pressurization is performed with hydrogen gas. In some embodiments, pressurization is performed with another suitable gas, such as an inert gas such as nitrogen, helium, or argon. In some embodiments, the method is performed at a pressure greater than 50 psi. In some embodiments, the method is performed at a pressure greater than 100 psi. In some embodiments, the method is performed at a pressure greater than 200 psi. In some embodiments, the method is performed at a pressure greater than 500 psi. In some embodiments, the method is performed at a pressure greater than 800 psi. In some embodiments, the method is performed at a pressure greater than 1000 psi.

In some embodiments, the method is performed at a pressure of 50 psi. In some embodiments, the method is performed at a pressure of 100 psi. In some embodiments, the method is performed at a pressure of 200 psi. In some embodiments, the method is performed at a pressure of 500 psi. In some embodiments, the method is performed at a pressure of 800 psi. In some embodiments, the method is performed at a pressure of 1000 psi. In some embodiments, the method is performed at a pressure of 14 bar. In some embodiments, the method is performed at a pressure of 35 bar. In some embodiments, the method is performed at a pressure of 55 bar.

In some embodiments, the method is performed at a pressure of less than 50 psi (but not zero). In some embodiments, the method is performed at a pressure of less than 100 psi (but not zero). In some embodiments, the method is performed at a pressure of less than 200 psi (but not zero). In some embodiments, the method is performed at a pressure of less than 500 psi (but not zero). In some embodiments, the method is performed at a pressure of less than 800 psi (but not zero). In some embodiments, the method is performed at a pressure of less than 1000 psi (but not zero).

In some embodiments of the present disclosure, the method is performed at a pressure between 50 psi and 1000 psi, or any number in between the aforementioned ranges. In some embodiments, the method is performed at a pressure between 100 psi and 500 psi, or any number between the aforementioned ranges. In some embodiments, the method is performed at a pressure between 200 psi and 525 psi, or any number between the aforementioned ranges. In some embodiments, the method is performed at a pressure between 500 psi and 1000 psi, or any number in between the aforementioned ranges. In some embodiments, the method is performed at a pressure between 150 psi and 600 psi, or any number between the aforementioned ranges. In some embodiments, the method is performed at a pressure between 300 psi and 550 psi, or any number in between the aforementioned ranges.

A method of making a purified FDCA pathway product can include performing the method for a specified amount of time. In some embodiments, the method is performed for more than 30 minutes. In some embodiments, the method is performed for more than 60 minutes. In some embodiments, the method is performed for greater than 120 minutes. In some embodiments, the method is performed for greater than 180 minutes. In some embodiments, the method is performed for greater than 240 minutes. In some embodiments, the method is performed for greater than 300 minutes.

In some embodiments, the method is performed for 30 minutes. In some embodiments, the method is performed for 60 minutes. In some embodiments, the method is performed for 120 minutes. In some embodiments, the method is performed for 180 minutes. In some embodiments, the method is performed for 240 minutes. In some embodiments, the method is performed for 300 minutes.

In some embodiments, the method is performed for less than 30 (but not zero) minutes. In some embodiments, the method is performed for less than 60 (but not zero) minutes. In some embodiments, the method is performed for less than 120 (but not zero) minutes. In some embodiments, the method is performed for less than 180 (but not zero) minutes. In some embodiments, the method is performed for less than 240 (but not zero) minutes. In some embodiments, the method is performed for less than 300 (but not zero) minutes.

In some embodiments, the method is performed for 30 minutes to 300 minutes, or any number of hours in between the aforementioned ranges. In some embodiments, the method is performed for 60 minutes to 240 minutes, or any number of hours in between the aforementioned ranges. In some embodiments, the method is performed for 60 minutes to 120 minutes, or any number of hours in between the aforementioned ranges. In some embodiments, the method is performed for 120 minutes to 180 minutes, or any number of hours in between the aforementioned ranges. In some embodiments, the method is performed for 60 minutes to 120 minutes, or any number of hours in between the aforementioned ranges. In some embodiments, the method is performed for 180 minutes to 240 minutes, or any number of hours in between the aforementioned ranges. In some embodiments, the method takes 2 to 4 hours, 2 to 6 hours, 3 to 8 hours, 5 to 10 hours, 8 to 12 hours, 10 to 15 hours, 12 to 20 hours, 15 to 24 hours, 1 to 2 hours. days, 1 to 3 days, 2 to 4 days, or any number of hours in between the aforementioned ranges.

In some embodiments, a method of making a purified FDCA pathway product comprises an FDCA pathway product comprising or consisting of FDCA and FFCA; hydrogen at a pressure in the range of 50-800 psi or any number in between; comprising or consisting of a reaction mixture comprising or consisting of a heterogeneous reduction catalyst comprising a solid support selected from the group of carbon, silicon dioxide, and/or Al ₂ O ₃ or mixtures thereof, wherein the heterogeneous reduction The catalyst may be a metal selected from Cu, Ni, Pd, Pt and/or Ru or a mixture thereof; and a multi-component solvent comprising water and a water-miscible aprotic organic solvent, wherein the water-miscible aprotic organic solvent comprises or consists of dioxane and/or sulfolane. In some embodiments, the temperature of the reaction mixture may be in the range of 60-140 °C or any number in between. In some embodiments, the reaction may proceed for a period ranging from 1-24 hours or any number of hours in between.

In some embodiments, a method of making a purified FDCA pathway product comprises a molar concentration of FDCA pathway product in the range of 0.1-3.5 M or any number therebetween, the FDCA pathway product comprising or consisting of FDCA and FFCA; hydrogen at a pressure in the range of 50-800 psi or any number in between; may comprise or consist of a reaction mixture comprising or consisting of a heterogeneous reduction catalyst in a weight ratio of catalyst:FDCA pathway product in the range of 1:0.04 to 1:1; wherein the heterogeneous reduction catalyst comprises a solid support selected from the group of carbon, silicon dioxide, and/or Al ₂ O ₃ or mixtures thereof, wherein the heterogeneous reduction catalyst is selected from Cu, Ni, Pd, Pt and/or Ru metals or mixtures thereof; and a multi-component solvent comprising water and a water-miscible aprotic organic solvent, wherein the water-miscible aprotic organic solvent comprises or consists of dioxane and/or sulfolane. The multi-component solvent may include water at a concentration ranging from 0.1-2.5 M or any number in between. In some embodiments, the temperature of the reaction mixture may be in the range of 60-140 °C or any number in between. In some embodiments, the reaction may proceed for a period ranging from 1 to 24 hours or any number of hours in between.

In some embodiments, a method of making a purified FDCA pathway product comprises an FDCA pathway product comprising or consisting of FDCA and FFCA; hydrogen at a pressure ranging from 50 to 800 psi or any number in between; a heterogeneous reduction catalyst comprising or consisting of Pd/C, Pt/C, Ru/C, Cu/Al ₂ O ₃ , and/or Ni/Al ₂ O ₃ or mixtures thereof; and a reaction mixture comprising or consisting of a multi-component solvent comprising water and a water-miscible aprotic organic solvent, wherein the water-miscible aprotic organic solvent comprises dioxane and/or sulfolane. or consist of In some embodiments, the temperature of the reaction mixture may be in the range of 60-140 °C or any number in between. In some embodiments, the reaction may proceed for a period ranging from 1-24 hours or any number of hours in between.

In some embodiments, a method of making a purified FDCA pathway product comprises a molar concentration of FDCA pathway product in the range of 0.1-3.5 M or any number therebetween, the FDCA pathway product comprising or consisting of FDCA and FFCA; hydrogen at a pressure in the range of 50-800 psi or any number in between; may comprise or consist of a reaction mixture comprising or consisting of a heterogeneous reduction catalyst in a weight ratio of catalyst:FDCA pathway product in the range of 1:0.04 to 1:1; wherein the heterogeneous reduction catalyst comprises Pd/C, Pt/C, Ru/C, Cu/Al ₂ O ₃ , and/or Ni/Al ₂ O ₃ or mixtures thereof, and water and water miscible aprotic organic solvents. wherein the water-miscible aprotic organic solvent comprises or consists of dioxane and/or sulfolane. The multi-component solvent may include water at a concentration ranging from 0.1-2.5 M or any number in between. In some embodiments, the temperature of the reaction mixture may be in the range of 60-140 °C or any number in between. In some embodiments, the reaction may proceed for a period ranging from 1-24 hours or any number of hours in between.

In some embodiments, the purified FDCA pathway product comprises FDCA, HMFCA, MFA with less than 10% molar impurity, and THFDCA with less than 10% molar impurity.

In some embodiments, the purified FDCA pathway product comprises greater than 90% FDCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises greater than 95% FDCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises greater than 99% FDCA on a molar purity basis.

In some embodiments, the purified FDCA pathway product comprises 90% to 99% by molar purity, or any number between the aforementioned ranges, of FDCA. In some embodiments, the purified FDCA pathway product comprises 95% to 99% by molar purity, or any number between the aforementioned ranges, of FDCA. In some embodiments, the purified FDCA pathway product comprises 90% to 95% by molar purity, or any number between the aforementioned ranges, of FDCA.

In some embodiments, the purified FDCA pathway product comprises less than 5% FFCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 1% FFCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.5% FFCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.1% FFCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.05% FFCA on a molar purity basis.

In some embodiments, the purified FDCA pathway product comprises from 0.05% to 5%, on a molar purity basis, or any number between the aforementioned ranges of FFCA. In some embodiments, the purified FDCA pathway product comprises from 0.1% to 1%, on a molar purity basis, or any number between the aforementioned ranges of FFCA. In some embodiments, the purified FDCA pathway product comprises from 0.05% to 0.5%, on a molar purity basis, or any number between the aforementioned ranges of FFCA. In some embodiments, the purified FDCA pathway product comprises 0.5% to 1%, on a molar purity basis, or any number between the aforementioned ranges of FFCA. In some embodiments, the purified FDCA pathway product comprises from 1% to 5%, on a molar purity basis, or any number between the aforementioned ranges of FFCA.

In some embodiments, the purified FDCA pathway product comprises less than 5% MFA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 1% MFA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.5% MFA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.1% MFA on a molar purity basis.

In some embodiments, the purified FDCA pathway product comprises from 0.1% to 5%, or any number between the aforementioned ranges, of MFA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises from 0.1% to 1%, or any number between the aforementioned ranges, of MFA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises from 0.1% to 0.5%, on a molar purity basis, or any number between the aforementioned ranges of MFA. In some embodiments, the purified FDCA pathway product comprises 0.5% to 1%, or any number between the aforementioned ranges, of MFA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises from 1% to 5%, on a molar purity basis, or any number between the aforementioned ranges of MFA.

In some embodiments, the purified FDCA pathway product comprises less than 1% THFDCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.9% THFDCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.5% THFDCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.1% THFDCA on a molar purity basis.

In some embodiments, the purified FDCA pathway product comprises 0.1% to 1%, or any number between the aforementioned ranges, of THFDCA on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises from 0.1% to 0.9% on a molar purity basis, or any number between the aforementioned ranges, of THFDCA. In some embodiments, the purified FDCA pathway product comprises from 0.1% to 0.5% on a molar purity basis, or any number between the aforementioned ranges, of THFDCA. In some embodiments, the purified FDCA pathway product comprises from 0.5% to 0.9% on a molar purity basis, or any number between the aforementioned ranges, of THFDCA. In some embodiments, the purified FDCA pathway product comprises 0.9% to 1%, or any number between the aforementioned ranges, of THFDCA on a molar purity basis.

In the methods described herein, the purified FDCA pathway product may further include HMFCA reduced from FFCA. In some embodiments, the yield of reduced HMFCA from FFCA is greater than 25%. In some embodiments, the yield of reduced HMFCA from FFCA is greater than 40%. In some embodiments, the yield of reduced HMFCA from FFCA is greater than 75%. In some embodiments, the yield of reduced HMFCA from FFCA is greater than 90%. In some embodiments, the yield of reduced HMFCA from FFCA is greater than 95%. In some embodiments, the yield of reduced HMFCA from FFCA is greater than 99%.

In some embodiments, the yield of reduced HMFCA from FFCA is between 25% and 99%, or any number in between the aforementioned ranges. In some embodiments, the yield of reduced HMFCA from FFCA is between 40% and 99%, or any number in between the aforementioned ranges. In some embodiments, the yield of reduced HMFCA from FFCA is between 75% and 99%, or any number in between the aforementioned ranges. In some embodiments, the yield of reduced HMFCA from FFCA is between 90% and 99%, or any number in between the aforementioned ranges. In some embodiments, the yield of reduced HMFCA from FFCA is between 95% and 99%, or any number in between the aforementioned ranges. In some embodiments, the yield of reduced HMFCA from FFCA is between 90% and 95%, or any number in between the aforementioned ranges.

In some embodiments, the purified FDCA pathway product comprises less than 10% DDF on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 5% DDF on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 1% DDF on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.5% DDF on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises less than 0.1% DDF on a molar purity basis.

In some embodiments, the purified FDCA pathway product comprises from 0.1% to 10%, on a molar purity basis, or any number between the aforementioned ranges of DDF. In some embodiments, the purified FDCA pathway product comprises from 0.1% to 5%, or any number between the aforementioned ranges, of DDF on a molar purity basis. In some embodiments, the purified FDCA pathway product comprises from 0.1% to 1%, or any number between the aforementioned ranges, of DDF on a molar purity basis.

III. Crystallization of purified FDCA pathway products

Purified FDCA pathway products prepared by the methods described in Section II of this application may be further purified. In some embodiments, the purified FDCA pathway product is further purified by crystallization. Applicants advantageously find that reduction of FFCA to HMFCA in FDCA pathway products makes it easier to remove HMFCA from purified FDCA pathway products via crystallization than attempting to remove FFCA from FDCA pathway products via crystallization alone. Found.

In some embodiments, the crystallization solution is the same multi-component solvent used in the process of making the purified FDCA pathway product.

Solution phase crystallization is typically performed by introducing a saturated (or supersaturated) solution of the purified PFCA pathway product into a crystallizer where the solution is subjected to crystallization conditions, and crystallization is accomplished by, for example, reducing the temperature or evaporating the solvent. (e.g., solvent removal), or a combination of the two. Solvent evaporation can be used to concentrate the solution to initiate crystallization, and can also be used to adjust the solvent composition to reduce the solubility of the purified FDCA pathway product.

In one embodiment, when the crystallization conditions include temperature adjustment, the present disclosure

ranges from 50°C to 220°C or any number in between, such as 50, 60, 70, 80, 90, 100, 110, 115, 120, 130, 140, 150, 160, 180, 190, 200, 210, or providing a crystallization solution comprising a purified FDCA pathway product and a crystallization solvent at a first temperature of 220° C. or within a range defined by any two temperatures noted above; and

cooling the crystallization solution to a second temperature lower than the first temperature to form a plurality of FDCA crystals of different particle sizes;

It provides a method for preparing a crystalline FDCA preparation comprising a.

Cooling reduces the solubility of the FDCA pathway products in the crystallization solvent, allowing crystals of FDCA to form in solution. The first temperature typically ranges from 60° C. to 180° C. or any number in between, such as for example 60, 70, 80, 90, 100, 110, 115, 120, 130, 140, 150, 160, or 180 °C, or within the range defined by any two temperatures mentioned above. In some embodiments, the first temperature ranges from 70°C to 150°C or any number in between, such as 70, 80, 90, 100, 110, 115, 120, 130, 140, or 150°C, or as noted above. within the range defined by any two temperatures. When the crystallization solution is cooled, it is typically at or below 60°C, such as for example up to 60, 50, 40, 30, 20, 10, 5, or 0°C, or by any two temperatures mentioned above. It is cooled to a temperature within a defined range. More typically, it is defined by a temperature of less than or equal to 50°C or less than or equal to 40°C, such as for example less than or equal to 50, 40, 30, 20, 10, 5, or 0°C, or any two of the above mentioned temperatures. cooled to a temperature within the range

In embodiments in which solvent removal (evaporation) is used to initiate crystallization, the present disclosure provides

(a) providing a first crystallization solution comprising a purified FDCA pathway product and a first crystallization solvent selected from the group consisting of water, organic solvents and combinations thereof;

(b) removing a first portion of the first crystallization solvent from the first crystallization solution to produce a first purified FDCA pathway product slurry, wherein the first purified FDCA pathway product slurry comprises a first plurality of FDCA crystals and a second portion of the first crystallization solvent; and

(c) separating the first plurality of FDCA crystals from the second portion of the first crystallization solvent;

It provides a method for preparing a crystalline FDCA preparation comprising a.

In a further embodiment, the first plurality of FDCA determinations comprise the additional steps of:

(d) dissolving the first plurality of FDCA crystals in a second crystallization solvent to produce a second crystallization solution comprising FDCA and the second crystallization solvent; and

(e) removing a first portion of the second crystallization solvent from the second crystallization solution to produce a second FDCA slurry, wherein the second FDCA slurry comprises a second plurality of FDCA crystals and a second portion of the second crystallization solvent. comprising a part; and

(f) separating a second plurality of FDCA crystals from a second portion of a second crystallization solvent;

It is recrystallized by performing

Partial removal of the crystallization solvent can be achieved using known methods for removing solvent from solutions, such as evaporation, distillation, and the like. Solvent removal is facilitated by raising the temperature of the crystallization solution to effect vaporization of the crystallization solvent or its components, so that one portion of the crystallization solvent is present in the liquid phase and another portion is present in the vapor phase to remove it. it can be done Solvent removal increases the concentration of the purified FDCA pathway product, causing it to crystallize, thereby providing a slurry of FDCA crystals in a continuous liquid phase. Often, one or both of the first and second crystallization solvents are multi-component solvents, wherein the removal of a first portion of the first and/or second crystallization solvents removes all or part of one of the components of the multi-component solvent while removing , which may include little or no removal of other components. In these embodiments, the multi-component solvent may include one organic solvent species that is a light organic solvent and a second organic species that is a heavy organic solvent; Or alternatively, it may include water and an organic solvent that is a heavy or light water-miscible organic solvent.

Separation of the first plurality of FDCA crystals and the second plurality of FDCA crystals from the second portion of the first crystallization solvent and the second portion of the second crystallization solvent, respectively, is a known method for separating a solid from a liquid. This can be achieved using methods such as filtration, centrifugation, and the like.

The dissolution step (steps (a and d)) is typically carried out at an elevated temperature to facilitate dissolution of the first FDCA crystals in the second crystallization solvent. The temperature will depend on the crystallization solvent used, but can be readily determined by raising the temperature until the first plurality of FDCA crystals are completely dissolved, and optionally adding additional second crystallization solvent. Typically, the dissolution step ranges from 50°C to 220°C or any number in between, such as 50, 60, 70, 80, 90, 100, 110, 115, 120, 130, 140, 150, 160, 180, at a temperature of 190, 200, 210, or 220° C., or within a range defined by any two temperatures mentioned above. Often, the dissolution step is in the range of 60°C to 180°C or any number in between, or in the range of 70°C to 150°C or any number in between, such as 60, 70, 80, 90, 100, 110, 115, 120, 130, 140, 150, 160, 170, or 180° C., or within a range defined by any two temperatures mentioned above. In some embodiments, the dissolution step is at the higher end of these ranges, such as in the range of 100°C to 220°C or any number in between, or in the range of 150°C to 220°C or any number in between, such as 100, 110, 115, 120, 130, 140, 150, 160, 180, 190, 200, 210, or 220° C., or within a range defined by any two temperatures noted above.

The first and second crystallization solvents may be the same or different. In certain embodiments, at least one of the first and second crystallization solvents is a multi-component solvent comprising component solvent species common to both crystallization solvents. In some embodiments, the first crystallization solution comprising a purified FDCA pathway product is a multi-component solvent used in a method of making a purified FDCA pathway product as described above. In some embodiments, the first crystallization solvent is not the same as the multi-component solvent used in the previous reduction step. In these embodiments, all or part of the multi-component solvent may be removed prior to the crystallization step, for example by evaporation or the like. The resulting solid is in a different solvent (e.g., water or a different organic solvent species) or a different multi-component solvent (e.g., a solvent that does not have the same composition as the multi-component solvent from the method of making the purified FDCA pathway product). It can be dissolved to prepare a first crystallization solution.

Crystallization of the purified FDCA product may further include dissolving the purified FDCA product in any subsequent number of crystallization solvents (eg, a third, fourth, fifth or sixth crystallization solvent). In some embodiments, the subsequent crystallization solvent can be the same as or different from those described above for the first and/or second crystallization solvent. In some embodiments, the subsequent crystallization method may be the same as or different from that described above for the first and/or second crystallization solvent.

In a specific embodiment, the crystallization solvent is a multi-component solvent comprising water and a water-miscible organic solvent. Accordingly, in a further embodiment, the present disclosure provides

providing a crystallization solution comprising a purified FDCA pathway product and a crystallization solvent that is a multi-component solvent comprising water and a water-miscible organic solvent;

Initiating crystallization of the purified FDCA pathway product; and

generating a plurality of purified FDCA pathway product crystals of different particle sizes.

It provides a method for preparing a crystalline preparation of a purified FDCA pathway product comprising a.

In this embodiment, the water-miscible organic solvent is typically a water-miscible aprotic organic solvent. In an exemplary embodiment, the water miscible aprotic organic solvent is an ether such as dioxane, dioxolane, and/or diglyme or mixtures thereof. To illustrate the benefits of this solvent system, the FDCA solubility relationship comparing representative solvent compositions of the present disclosure to water, dioxane, dioxolane (eg, 1,3-dioxolane), and/or diglyme is shown below. are discussed The high solubility of FDCA in the solvent composition of the present disclosure enables preparation of saturated solutions of FDCA in formulations for purification by crystallization. By removing water or an organic solvent (or an azeotrope of water and an organic solvent) to adjust the solvent composition, the organic solvent-rich solvent composition (if the selected organic solvent is less volatile than water), or the water-rich solvent composition (selected organic solvent if the solvent is more volatile than water). FDCA is significantly less soluble in water or organic solvents than the solvent compositions of the present disclosure. A saturated solution of FDCA can be subjected to crystallization conditions by reducing the temperature or by evaporating the solvent to adjust the solvent composition, or both.

Exemplary water-miscible aprotic solvents suitable for use in the crystallization methods of the present disclosure are tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2 -pyrrolidone ("NMP"), methyl ethyl ketone ("MEK"), and/or gamma-valerolactone or any mixture thereof. Preferably, the water-miscible aprotic organic solvent is an ether such as, for example, glyme, dioxane (eg 1,4-dioxane), dioxolane (eg 1,3-dioxolane), and/or tetrahydrofuran or any mixture thereof. Glymes suitable for use in the practice of the present disclosure include, for example, monoglyme (1,2-dimethoxyethane, “DME”), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme, polyglyme, and/or highly ethoxylated diethers of high molecular weight alcohols ("hyglyme") or any mixtures thereof. Often, the water-miscible aprotic organic solvent is glyme, diglyme, or dioxane or any mixture thereof.

In some embodiments, the water-miscible organic solvent species comprises at least 5 vol%, at least 10 vol%, at least 15 vol%, at least 20 vol%, at least 25 vol%, at least 30 vol%, at least 35 vol% of the multi-component solvent , at least 40 vol%, at least 45 vol%, at least 50 vol%, at least 55 vol%, at least 60 vol%, at least 65 vol%, at least 70 vol%, at least 75 vol%, at least 80 vol%, at least 85 vol% , at least 90 vol%, or at least 95 vol%, or within the range defined by any two values noted above; Correspondingly, water typically accounts for less than 95 vol%, less than 90 vol%, less than 85 vol%, less than 80 vol%, less than 75 vol%, less than 70 vol%, less than 65 vol%, respectively, of the multicomponent system. less than 60 vol%, less than 55 vol%, less than 50 vol%, less than 45 vol%, less than 40 vol%, less than 35 vol%, less than 30 vol%, less than 25 vol%, less than 20 vol%, less than 15 vol%, less than 10 vol%, or less than 5 vol% (but not zero), or within a range defined by any two values noted above.

In some embodiments, the multi-component solvent comprises from 1 to 5 weight percent of water or any number therebetween and from 99 to 95 weight percent or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 5 to 10 weight percent of water or any number therebetween and from 95 to 90 weight percent or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 10 to 15% by weight of water or any number therebetween and from 90 to 85% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 15 to 20% by weight of water or any number therebetween and from 85 to 80% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 20 to 25% by weight of water or any number therebetween and from 80 to 75% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 25 to 30% by weight of water or any number therebetween and from 75 to 70% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 30 to 35% by weight of water or any number therebetween and from 70 to 65% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises in the range of 35 to 40% by weight or any number therebetween of water and in the range of 65 to 60% by weight or in between any number of water miscible organic solvents. In some embodiments, the multi-component solvent comprises from 40 to 45% by weight of water or any number therebetween and from 60 to 55% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 45 to 50% by weight of water or any number therebetween and from 65 to 50% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 50 to 55% by weight of water or any number therebetween and from 50 to 45% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 55 to 60% by weight of water or any number therebetween and from 45 to 40% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 60 to 65% by weight of water or any number therebetween and from 40 to 35% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 65 to 70% by weight of water or any number therebetween and from 35 to 30% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 70 to 75% by weight of water or any number therebetween and from 30 to 25% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 75 to 80% by weight of water or any number therebetween and from 25 to 20% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 80 to 85% by weight of water or any number therebetween and from 20 to 15% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 85 to 90% by weight of water or any number therebetween and from 15 to 10% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 90 to 95% by weight of water or any number therebetween and from 10 to 5% by weight or any number therebetween of a water-miscible organic solvent. In some embodiments, the multi-component solvent comprises from 95 to 99% by weight of water or any number therebetween and from 5 to 1% by weight or any number therebetween of a water-miscible organic solvent.

More typically, the volume ratio of water to water-miscible organic solvent typically ranges from 1:6 to 6:1 (v:v) or any number in between. In some embodiments, the volume ratio is from 1:4 to 4:1 (v:v) or any number in between. In some embodiments, the volume ratio is from 1:4 to 3:1 (v:v) or any number of water:water miscible organic solvents in between. In some embodiments, the volume ratio is from 1:4 to 1:3 (v:v) or any number of water:water miscible organic solvents in between. In certain embodiments, the volume ratio is a 1:1 (v:v) water:water miscible organic solvent.

Crystallization can be initiated using the temperature reduction (cooling) or solvent removal methods described above. When a decrease in temperature is used to initiate crystallization, typically the temperature of the crystallization solution is typically in the range of 60°C to 220°C or any number in between, such as 60, 70, 80, 90, 100, 110, 115, from a first temperature of 120, 130, 140, 150, 160, 180, 190, 200, 210, or 220° C., or within a range defined by any two temperatures noted above. When water is a component of the crystallization solvent, the first temperature is often at the upper end of this range, for example in the range of 100°C to 220°C or any number in between or in the range of 150°C to 220°C or in between. to any number of, such as 100, 110, 115, 120, 130, 140, 150, 160, 180, 190, 200, 210, or 220 °C, or within a range defined by any two temperatures noted above. . In some embodiments, the first temperature ranges from 60°C to 180°C or any number in between, such as 60, 70, 80, 90, 100, 110, 115, 120, 130, 140, 150, 160, or 180 °C, or within the range defined by any two temperatures mentioned above, the second temperature being lower than the first temperature. In some embodiments, the first temperature ranges from 70°C to 150°C or any number in between, such as 70, 80, 90, 100, 110, 115, 120, 130, 140, or 150°C, or as noted above. within the range defined by any two temperatures. When the crystallization solution is cooled, it is typically less than 60°C, such as 60, 50, 40, 30, 20, 10, 5, or 0°C, or within the range defined by any two temperatures mentioned above. cooled to the second temperature. More typically, it is a second temperature that is less than 50°C or less than 40°C, such as less than or equal to 50, 40, 30, 20, 10, 5, or 0°C, or within a range defined by any two temperatures noted above. cooled with

Crystallization also removes a first portion of the crystallization solution from the crystallization solution to produce a purified FDCA pathway product slurry, wherein the purified FDCA pathway product comprises a first plurality of FDCA crystals of different particle sizes and a second portion of the crystallization solvent. contains a portion; It may begin by separating a plurality of FDCA crystals from the second portion of the first crystallization solvent. A first plurality of FDCA crystals may optionally be dissolved in the same or different crystallization solvents, and the process may be repeated to obtain a second plurality of FDCA crystals of different particle sizes.

Seed crystals of purified FDCA pathway product may be added to further promote initiation of crystallization. Other additives, such as anti-foaming agents or crystallization aids, may be added to the crystallization solution to facilitate the crystallization process and enable the formation of a suspension containing FDCA crystals. Antifoaming agents suitable for use in the practice of the present disclosure include, for example, silicones, surfactants, phosphates, alcohols, glycols, stearates, and the like. Additives such as surfactants or electrolyte polymers can also affect the morphology and composition of the crystals formed. See, eg, US 5,296,639 and US 6,534,680, which are expressly incorporated herein by reference in their entirety. Other additives may function as flow enhancers to prevent flocculation of the crystalline product on storage (see eg US 6,534,680).

FDCA crystals produced by the methods described herein can be separated from solution (mother liquor) by centrifugation, filtration, or other suitable method for separating solids from liquids. The crystals may then be washed and dried using any suitable method known to those skilled in the art.

The crystallization methods described herein can be performed as part of an integrated process for the production of FDCA crystals from raw feeds comprising purified FDCA pathway products. The set of method steps can be performed in at least a first crystallization zone, a dissolution zone, and a second (refining) crystallization zone. The crystallization process can also be performed as part of an integrated process for the production of FDCA crystals from a purified FDCA pathway product feedstock comprising an FDCA pathway product and a multi-component solvent. In this method, the integrated crystallization method is further integrated with the reduction reaction method described herein. In this integrated process, the effluent from at least one reduction reaction zone is passed as feedstock into the integrated crystallization process. In the crystallization methods described herein, a crystal separation operation (such as the use of a centrifuge) may optionally be placed after each crystallization zone (eg between the crystallization zone and the next dissolution zone).

In some embodiments, the crystalline FDCA comprises at least 98% by weight FDCA, more typically it comprises at least 99% by weight FDCA, and in some embodiments it comprises greater than 99% by weight FDCA.

In some embodiments, crystalline FDCA comprises greater than 99% molar purity FDCA. In some embodiments, the crystalline FDCA preparation comprises greater than 99.5% molar purity FDCA. In some embodiments, the crystalline FDCA preparation comprises greater than 99.8% molar purity FDCA. In some embodiments, the crystalline FDCA preparation comprises greater than 99.9% molar purity FDCA. In some embodiments, the crystalline FDCA preparation comprises greater than 99.95% molar purity FDCA. In some embodiments, the crystalline FDCA preparation comprises greater than 99.99% molar purity FDCA. In some embodiments, the crystalline FDCA preparation does not contain detectable levels of impurities.

The crystallization methods of the present disclosure can be performed using known industrial crystallizer systems suitable for performing solution phase crystallization. Suitable systems include, for example, batch crystallizers, continuous crystallizers (eg, forced circulation crystallizers, draft-tube crystallizers, draft-tube-baffle crystallizers, or Oslo-type crystallizers). etc.), and other such crystallizer systems.

Crystalline FDCA formulations of the present disclosure are typically dry and contain less than 1% water by weight. Often, they are less than 0.9%, or less than 0.8%, or less than 0.7%, or less than 0.6%, or less than 0.5%, or less than 0.4%, or less than 0.3%, or less than 0.2%. water or water in an amount within a range defined by any two amounts mentioned above.

The disclosed methods can be performed on many scales. In some embodiments, the method can be performed on a small scale such that the amount of compound used is in the milligram to gram range. In some embodiments, the method can be performed on an industrial scale. In some embodiments, the industrial scale process can be performed in multiple batches, where multiple batches of FDCA pathway product, purified FDCA pathway product, and/or crystallized FDCA are obtained. In some embodiments, an industrial scale process can be performed as a continuous process in which the FDCA pathway product, purified FDCA pathway product, and/or crystallized FDCA are continuously fluidly connected.

The methods of the present disclosure may be batch, semi-batch, or continuous using reactors known in the art, such as, for example, fixed bed reactors, trickle bed reactors, slurry phase reactors, moving bed reactors, and the like. It can be carried out in a fixed flow reactor or format.

IV. Reduction Catalyst Example

Additional alternatives are described in further detail in the examples below, which in no way limit the claimed scope.

Example 1

Catalyst tests were performed in 1 ml glass vials housed in 96-well inserts placed in high pressure high throughput reactors. Diamond, GM, Murphy, V., Boussie, TR, in Modern Applications of High Throughput R&D in Heterogeneous Catalysis, (eds, Hagemeyer, A. and Volpe, A. Jr. Bentham Science Publishers 2014, Chapter 8, 299- 309); See also US 8,669,397, both of which are incorporated herein by reference. Up to 20 mg of each powder catalyst was mixed with 0.25 mL of a solution prepared from a 3:2 (wt/wt) dioxane:H ₂ O mixture in varying amounts of 5-formyl-2-furoic acid (FFCA) and 2, It was placed in a reactor along with 5-furandicarboxylic acid (FDCA). The 1 ml reaction vials in the inserts were each covered with a Teflon sheet, a silicon mat and a steel gas diffusion plate (each containing pin-holes to allow gas introduction). The insert was placed in a pressure vessel and it was leak tested under nitrogen pressure. The atmosphere in the reactor is then replaced with hydrogen at the target pressure (e.g. 500 psig), the reactor is heated to the target temperature (e.g. 100° C.) and heated to 800 °C for a specified period of time (e.g. 60 minutes). Shake at rpm. After the reaction was complete, shaking was stopped and the reactor was allowed to cool to room temperature. Samples were prepared for HPLC analysis by sampling from each reactor after diluting with dimethyl sulfoxide (DMSO) and H ₂ O. The reaction products were hydroxymethylfurancarboxylic acid (HMFCA) and 5-methyl-2-furoic acid (MFA) from hydrogenation of FFCA, and tetrahydrofuran dicarboxylic acid (THFDCA) from hydrogenation of FDCA. The yields of HMFCA and MFA were calculated based on the amount of FFCA used, while the yield of THFDCA was calculated based on the amount of FDCA used.

All catalysts were commercially available and screened as powders. If powder was not available, the extrudate catalyst was ground into powder prior to the hydrogenation reaction. Cu Clariant T-4874 was a powder from the extrudate Cu Catalyst Clariant T-4874 after rinsing the stabilizing solution iso-decanol with dioxane. Ni JM HTC 500RP was a powder from extrudate Ni catalyst Johnson Matthey, Inc. HTC 500RP. Catalyst Pd/C JM-10 (A102038-5 Lot# C-9074), Pd/C JM-4 (A405032-5 Lot# C-9191), Ru/C JM-37 (D101023-5 Lot# C-9219 ), and Ru/C JM-38 (D101038-5 Lot# C-9220) were obtained from Johnson Matthey, Inc. and were used as such. Catalysts Ru/C JM-37* and Ru/C JM-38* are Ru/C JM-37 (D101023-5 Lot# C-9219) and Ru/C JM-38 (D101038-5 Lot) from Johnson Matthey Inc. # C-9220) (350° C. in forming gas for 3 hours). Results are presented in Table 1.

Table 1. Catalyst composition and performance in hydrogenation of FFCA and FDCA.

Example 2

20 mg of different powdered catalysts were placed in a separate reaction vessel together with a solution containing 0.6 M FFCA in 3:2 (wt/wt) dioxane:H ₂ O. Powdered catalysts were Cu BASF 0602 ^* (reduced in-house), Cu Clariant T-4874, Cu Clariant T-4874* (reduced in-house), Ni JM HTC 500 RP, Pd/C JM-4, Pd/C JM- 6, Pd/C JM-10, Pt/C JM-24, Pt/C JM-27, Ru/C JM-37, Ru/C JM-38 and no catalyst control. Catalysts Cu BASF 0602 ^* and Cu Clariant T-4874* were used in further reduced form (350° C. in forming gas for 3 hours). Each reaction vessel was pressurized with hydrogen at a target pressure of 55 bar. The reaction vessel was heated to a target temperature of 70°C and shaken for 2 hours, or alternatively, the reaction vessel was heated to a target temperature of 100°C and shaken for 1 hour. After the reaction was complete, shaking was stopped and the reactor was allowed to cool to room temperature.

HMFCA selectivity and FFCA conversion were calculated. Results are presented in FIG. 1 .

The yield of HMFCA and MFA, the amount of residual FFCA and mass balance were calculated. Results are presented in FIG. 2 .

Example 3

20 mg of different powdered catalysts were placed in a separate reaction vessel together with a solution containing 0.6 M FDCA in 3:2 (wt/wt) dioxane:H ₂ O. Supplied catalysts were Cu BASF 0602 ^* (reduced in-house), Cu Clariant T-4874, Cu Clariant T-4874* (reduced in-house), Ni JM HTC 500 RP, Pd/C JM-4, Pd/C JM- 6, Pd/C JM-10, Pt/C JM-24, Pt/C JM-27, Ru/C JM-37, Ru/C JM-38 and no catalyst control. Catalysts Cu BASF 0602 ^* and Cu Clariant T-4874* were used in further reduced form (350° C. in forming gas for 3 hours). Each reaction vessel was pressurized with hydrogen at a target pressure of 55 bar. The reaction vessel was heated to a target temperature of 70°C and shaken for 2 hours, or alternatively, the reaction vessel was heated to a target temperature of 100°C and shaken for 1 hour. After the reaction was complete, shaking was stopped and the reactor was allowed to cool to room temperature. The yield of THFDCA and the amount of residual FFCA, and mass balance were calculated. Results are presented in FIG. 3 .

Example 4

20 mg of different powdered catalysts were placed in a separate reaction vessel together with a solution containing 0.6 M FDCA and 0.6 M FFCA in 3:2 (wt/wt) dioxane:H ₂ O. Supplied catalysts were Cu BASF 0602 ^* (reduced in-house), Cu Clariant T-4874, Cu Clariant T-4874* (reduced in-house), Ni JM HTC 500 RP, Pd/C JM-4, Pd/C JM- 6, Pd/C JM-10, Pt/C JM-24, Pt/C JM-27, Ru/C JM-37, Ru/C JM-38 and no catalyst control. Catalysts Cu BASF 0602 ^* and Cu Clariant T-4874* were used in further reduced form (350° C. in forming gas for 3 hours). Each reaction vessel was pressurized with hydrogen at a target pressure of 55 bar. The reaction vessel was heated to a target temperature of 70°C and shaken for 2 hours, or alternatively, the reaction vessel was heated to a target temperature of 100°C and shaken for 1 hour. After the reaction was complete, shaking was stopped and the reactor was allowed to cool to room temperature.

HMFCA selectivity and FFCA conversion were calculated. Results are presented in FIG. 4 .

Yields of HMFCA, MFA and THFDCA, residual FFCA and FDCA amounts, and mass balance were calculated. Results are presented in FIG. 5 .

Example 5

2 mg and 5 mg of each Ni, Ru and Pd powdered catalyst were placed in a separate reaction vessel together with a solution containing 0.02 M FFCA and 0.38 M FDCA in 3:2 (wt/wt) dioxane:H ₂ O. Ni, Ru and Pd powdered catalysts are Ni JM HTC 500 RP, Pd/C JM-3, Pd/C JM-4, Pd/C JM-5, Ru/C JM-37*, Ru/C JM-38 * and no catalyst control. Catalysts Ru/C JM-37* and Ru/C JM-38* were used in further reduced form (350° C. in forming gas for 3 hours). Separately, 2 mg, 5 mg, 10 mg, and 15 mg of Cu Clariant T-4874 were added to a separate reaction vessel containing 0.02 M FDCA and 0.38 M FFCA in 3:2 (wt/wt) dioxane:H ₂ O. added with the solution.

Ni, Ru and Pd powdering catalytic reactions were tested with hydrogen at 14 and 35 bar, respectively. The Ni, Ru and Pd powdered catalyst reactants were heated to a target temperature of 70°C and agitated for 2 hours, or alternatively heated to a target temperature of 100°C and shaken for 1 hour.

The Cu powdering catalytic reaction was tested with hydrogen at 35 and 55 bar, respectively. The Cu powdering reaction was heated to a target temperature of 100°C and shaken for 1 hour, or alternatively, heated to a target temperature of 125°C and shaken for 1 hour.

After each reaction was complete, shaking was stopped and the reactor was cooled to room temperature. HMFCA selectivity was calculated as follows:

Results are presented in FIG. 6 .

The yields of HMFCA, MFA and THFDCA, the amount of residual FFCA and FDCA, and the mass balance of FFCA and FDCA were calculated for the Ni, Pd and Ru catalysts. Results are presented in FIG. 7 . In FIG. 7, a smaller marker size indicates a reaction vessel loaded with 2 mg of powdered catalyst and a larger marker size indicates a reaction vessel loaded with 5 mg of powdered catalyst.

The yields of HMFCA, MFA and THFDCA, the amount of residual FFCA and FDCA, and the mass balance of FFCA and FDCA were calculated for the Cu catalyst. Results are presented in FIG. 8 . 8, the smallest marker size represents the reaction vessel loaded with 2 mg of Cu powder catalyst, the second smallest marker size represents the reaction vessel loaded with 5 mg of Cu powder catalyst, and the third smallest marker size The reaction vessel loaded with 10 mg of Cu powder catalyst is shown, and the largest marker size represents the reaction vessel loaded with 15 mg of Cu powder catalyst.

Example 6

5 mg of different powdered catalysts were each placed in a separate reaction vessel together with 0.25 ml of a solution containing 0.020 M FFCA and 0.38 M FDCA in 3:2 (wt/wt) dioxane:H ₂ O. Powdered catalysts were Cu T-4874, Pd/C JM-10, and Ru/C JM-37*. Ru/C JM-37* was used in a further reduced form (350° C. in forming gas for 3 hours). Each reaction vessel was pressurized with hydrogen at a target pressure of 50 psi. The reaction vessel was shaken at room temperature for 4 hours. After the reaction was complete, shaking was stopped and adsorption on the catalyst was checked. The mass balance of FFCA and FDCA was calculated. Results are presented in Table 2.

Table 2.

Example 7

2 mg or 5 mg of Pd/C JM-9 powder catalyst was prepared in a 3:2 (wt/wt) dioxane:H ₂ O mixture containing 0.020 M FFCA (0.60 mg) and 0.38 M FDCA (12.0 mg). into the reaction vessel along with 0.25 mL of the containing solution. The reaction vessel was pressurized with hydrogen at a target pressure of 50 psi. The reaction vessel was heated to a target temperature of 50°C and shaken for 4 hours, or alternatively, the reaction vessel was heated to a target temperature of 70°C and shaken for 2 hours. After the reaction was complete, shaking was stopped and the reactor was allowed to cool to room temperature. The yields of HMF, HMFCA, MFA and THFDCA, the amount of residual FFCA and FDCA, and the mass balance of FFCA and FDCA were calculated. Results are presented in FIG. 9 .

Example 8

2 mg or 5 mg of Pd/C JM-10 powder catalyst was prepared in a 3:2 (wt/wt) dioxane:H ₂ O mixture containing 0.020 M FFCA (0.60 mg) and 0.38 M FDCA (12.0 mg). into the reaction vessel along with 0.25 mL of the containing solution. The reaction vessel was pressurized with hydrogen at a target pressure of 50 psi. The reaction vessel was heated to a target temperature of 50°C and shaken for 4 hours, or alternatively, the reaction vessel was heated to a target temperature of 70°C and shaken for 2 hours. After the reaction was complete, shaking was stopped and the reactor was allowed to cool to room temperature. The yields of HMF, HMFCA, MFA and THFDCA, the amount of residual FFCA and FDCA, and the mass balance of FFCA and FDCA were calculated. Results are presented in FIG. 10 .

Example 9

2 mg or 5 mg of Ru/C JM-37* powder catalyst was prepared in a 3:2 (wt/wt) dioxane:H ₂ O mixture and 0.020 M FFCA (0.60 mg) and 0.38 M FDCA (12.0 mg) into a reaction vessel with 0.25 mL of a solution containing Ru/C JM-37* was used in a further reduced form (350° C. in forming gas for 3 hours). The reaction vessel was pressurized with hydrogen at a target pressure of 50 psi. The reaction vessel was heated to a target temperature of 50°C and shaken for 4 hours, or alternatively, the reaction vessel was heated to a target temperature of 70°C and shaken for 2 hours. After the reaction was complete, shaking was stopped and the reactor was allowed to cool to room temperature. The yields of HMF, HMFCA, MFA and THFDCA, the amount of residual FFCA and FDCA, and the mass balance of FFCA and FDCA were calculated. Results are presented in FIG. 11 .

Example 10

2 mg or 5 mg of Ru/C JM-38* powdered catalyst was prepared in a 3:2 (wt/wt) dioxane:H ₂ O mixture and 0.020 M FFCA (0.60 mg) and 0.38 M FDCA (12.0 mg) into a reaction vessel with 0.25 mL of a solution containing Ru/C JM-38* was used in an additional reduced form (350° C. in forming gas for 3 hours). The reaction vessel was pressurized with hydrogen at a target pressure of 50 psi. The reaction vessel was heated to a target temperature of 50°C and shaken for 4 hours, or alternatively, the reaction vessel was heated to a target temperature of 70°C and shaken for 2 hours. After the reaction was complete, shaking was stopped and the reactor was allowed to cool to room temperature. The yields of HMF, HMFCA, MFA and THFDCA, the amount of residual FFCA and FDCA, and the mass balance of FFCA and FDCA were calculated. Results are presented in FIG. 12 .

V. Crystallization Examples

The purity (in weight percent) of FDCA (and residual HMFCA and FFCA) in the crystallized solids and mother liquor was determined using HPLC analysis with UV detection (λ = 254 nm), and the absorbance of FDCA, HMFCA and FFCA at 254 nm was correlated against calibration curves for FDCA, HMFCA and FFCA.

Example 11

FDCA (4.0 g) and HMFCA (0.21 g, FDCA:HMFCA 95:5 wt:wt) were suspended in 1,4-dioxane:water (40.4 g, 80:20 wt:wt). The stirred suspension was heated in an oil bath to 110-115° C. in a sealed reaction vial until all solids were dissolved. The heat was then turned off and the mixture was allowed to cool slowly to room temperature over 2 hours. The crystal suspension was stirred for an additional hour at room temperature. The crystals were filtered off and the mother liquor was collected. The crystals were dried under vacuum overnight to give FDCA (2.53 g, 63% yield, 99.42% purity) as white crystals. HMFCA 0.58% by weight according to HPLC analysis.

The mother liquor was evaporated under reduced pressure and the residual solid was dried under vacuum overnight to give FDCA:HMFCA (1.48 g, 88.6:11.4 wt:wt) as a pale yellow solid.

Total mass recovery: 4.01 g (95.2%).

Example 12

FDCA from Example 11 (2.47 g, FDCA:HMFCA 99.42:0.58 wt:wt) was suspended in 1,4-dioxane:water (22.3 g, 80:20 wt:wt). The stirred suspension was heated to 120° C. in an oil bath in a sealed reaction vial until all solids were dissolved. The heat was then turned off and the mixture was allowed to cool slowly to room temperature over 2 hours. The crystal suspension was stirred for an additional 2 hours at room temperature. The crystals were filtered off and the mother liquor was collected. The crystals were reslurried in demineralized water (10 mL) and filtered. The crystals were collected and dried under vacuum overnight to give FDCA (1.60 g, 65% yield, >99.95% purity) as white crystals. The amount of HMFCA was below detectable levels according to HPLC analysis.

The mother liquor was evaporated under reduced pressure and the residual solid was dried under vacuum overnight to give FDCA:HMFCA (0.71 g, 98.5:1.5 wt:wt) as an off-white solid.

Total mass recovery: 2.31 g (93.5%).

Example 13

FDCA (4.0 g) and HMFCA (0.21 g, FDCA:HMFCA 95:5 wt:wt) were suspended in 1,4-dioxane:water (40.4 g, 60:40 wt:wt). The stirred suspension was heated in an oil bath to 110-115° C. in a sealed reaction vial until all solids were dissolved. The heat was then turned off and the mixture was allowed to cool slowly to room temperature over 2 hours. The crystal suspension was stirred for an additional hour at room temperature. The crystals were filtered off and the mother liquor was collected. The crystals were dried under vacuum overnight to give FDCA (3.10 g, 78% yield, 99.56% purity) as white crystals. HMFCA 0.44% by weight, according to HPLC analysis.

The mother liquor was evaporated under reduced pressure and the remaining solid was dried under vacuum overnight to give FDCA:HMFCA (0.98 g, 82.2:17.8 wt:wt) as a pale yellow solid.

Total mass recovery, 4.08 g (96.9%).

Example 14

FDCA from Example 13 (3.05 g, FDCA:HMFCA 99.56:0.44 wt:wt) was suspended in 1,4-dioxane:water (27.4 g, 60:40 wt:wt). The stirred suspension was heated to 120° C. in an oil bath in a sealed reaction vial until all solids were dissolved. The heat was then turned off and the mixture was allowed to cool slowly to room temperature over 2 hours. The crystal suspension was stirred for an additional 2 hours at room temperature. The crystals were filtered off and the mother liquor was collected. The crystals were reslurried in demineralized water (10 mL) and filtered. The crystals were collected and dried under vacuum overnight to give FDCA (2.37 g, 78% yield, >99.95% purity) as white crystals. The amount of HMFCA was below detectable levels according to HPLC analysis.

The mother liquor was evaporated under reduced pressure and the remaining solid was dried under vacuum overnight to give FDCA:HMFCA (0.50 g, 98.0:2.0 wt:wt) as an off-white solid.

Total mass recovery, 2.87 g (94.1%).

Example 15

FDCA (3.06 g), HMFCA (0.148 g) and FFCA (12.9 mg, FDCA:HMFCA:FFCA 95:4.6:0.4 wt:wt:wt) were mixed with 1,4-dioxane:water (29.0 g, 60:40 wt :wt). The stirred suspension was heated to 120° C. in an oil bath in a sealed reaction vial until all solids were dissolved. The heat was then turned off and the mixture was allowed to cool slowly to room temperature over 2 hours. The crystal suspension was stirred for an additional hour at room temperature. The crystals were filtered off and the mother liquor was collected. The crystals were dried under vacuum overnight to give FDCA (2.42 g, 79% yield, 99.35% purity) as white crystals. 0.34 wt% HMFCA and 0.31 wt% FFCA, according to HPLC analysis.

The mother liquor was evaporated under reduced pressure and the remaining solid was dried under vacuum overnight to give FDCA:HMFCA:FFCA (0.64 g, 81.5:17.8:0.7: wt:wt:wt) as a pale yellow solid.

Total mass recovery, 3.06 g (94.8%).

Example 16

FDCA from Example 15 (2.27 g, FDCA:HMFCA:FFCA 99.35:0.34:0.31 wt:wt:wt) was suspended in 1,4-dioxane:water (20.5 g, 60:40 wt:wt). The stirred suspension was heated to 120° C. in an oil bath in a sealed reaction vial until all solids were dissolved. The heat was then turned off and the mixture was allowed to cool slowly to room temperature over 2 hours. The crystal suspension was stirred for an additional 2 hours at room temperature. The crystals were filtered off and the mother liquor was collected. The crystals were dried under vacuum overnight to give FDCA (1.78 g, 78% yield, 99.75% purity) as white crystals. 0.08% by weight HMFCA and 0.17% by weight FFCA according to HPLC analysis.

The mother liquor was evaporated under reduced pressure and the remaining solid was dried under vacuum overnight to give FDCA:HMFCA:FFCA (0.38 g, 97.6:1.6:0.8 wt:wt:wt) as an off-white solid.

Total mass recovery, 2.16 g (95.2%).

Example 17

FDCA from Example 16 (1.70 g, FDCA:HMFCA:FFCA 99.75:0.08:0.17 wt:wt:wt) was suspended in 1,4-dioxane:water (15.3 g, 60:40 wt:wt). The stirred suspension was heated to 120° C. in an oil bath in a sealed reaction vial until all solids were dissolved. The heat was then turned off and the mixture was allowed to cool slowly to room temperature over 2 hours. The crystal suspension was stirred for an additional hour at room temperature. The crystals were filtered off and the mother liquor was collected. The crystals were reslurried in demineralized water (10 mL) and filtered. The crystals were collected and dried under vacuum overnight to give FDCA (1.29 g, 76% yield, 99.91% purity) as white crystals. FFCA 0.09% by weight and HMFCA below detectable levels according to HPLC.

The mother liquor was evaporated under reduced pressure and the remaining solid was dried under vacuum overnight to give FDCA:HMFCA:FFCA (0.27 g, 99.4:0.1:0.5 wt:wt:wt) as a white solid.

Total mass recovery, 1.56 g (91.8%).

VI. Heterogeneous Oxidation Catalyst Examples

Example 18

Preparation of Pt/Bi on various solid supports

First, a metal precursor solution was prepared by mixing a solution of Bi(NO ₃ ) ₃ 5H ₂ O (43 wt% Bi) and Pt(NO ₃ ) _x (14.5 wt% Pt) in deionized water to prepare various solutions shown in Table 3. The Pt-Bi ratio was obtained. For example, to prepare the metal precursor solution used to form the catalyst in Example 1 of Table 3, 0.35 g of Bi(NO ₃ ) ₃ 5H ₂ O was dissolved in a Pt(NO ₃ ) _x solution in 3.0 mL of deionized water. Mixed with 2.05 mL. ZrO ₂ (Saint Gobain, BET specific surface area 40 m ² /g, particle size 75 to 150 μm), ZrO ₂ -TiO ₂ (40 wt% TiO ₂ , Saint-Gobain SZ 39140, BET) using the above solution Specific surface area 80 m ² /g, particle size 75 to 150 μm), TiO ₂ (Saint-Gobain ST 31119, BET specific surface area 40 m ² /g, particle size 75 to 150 μm), or silicon carbide (SiCat, BET specific surface area 25 m ² /g, particle size 150 to 250 μm) support was impregnated. After impregnation, the material was dried at 120° C. for 3 hours and then reduced at 350° C. for 3 hours under a flow of forming gas (5% H ₂ in N ₂ ).

Example 19

Preparation of Pt/Te on various solid supports

First, a metal precursor solution was prepared by mixing a solution of Te(OH) ₆ (55.6 wt% Te) and Pt(NO ₃ ) _x (14.5 wt% Pt) in deionized water to obtain various Pt-Te ratios shown in Table 3. got it ZrO ₂ (Saint-Gobain, BET specific surface area 40 m ² /g, particle size 75 to 150 μm), ZrO ₂ -TiO ₂ (40 wt% TiO ₂ , Saint-Gobain SZ 39140, BET specific surface area 80 m) ² /g, particle size 75 to 150 μm), TiO ₂ (Saint-Gobain ST 31119, BET specific surface area 40 m ² /g, particle size 75 to 150 μm), or silicon carbide (SiCat, BET specific surface area 25 m ² /g g, particle size 150 to 250 μm) was impregnated into the support. After impregnation, the material was dried at 120° C. for 3 hours and then reduced under a flow of forming gas (5% H ₂ in N ₂ ) at 350° C. for 3 hours.

Example 20

Preparation of Pt/Sn on various solid supports

First, metal precursor solutions were prepared by mixing solutions of Sn(oxalate)/hydrogen peroxide/citric acid (10.2 wt% Sn) and PtONO ₃ (62.5 wt% Pt) in deionized water to obtain various Pt-Sn ratios shown in Table 3. obtained. ZrO ₂ (Saint-Gobain, BET specific surface area 40 m ² /g, particle size 75 to 150 μm), ZrO ₂ -TiO ₂ (Saint-Gobain 40% by weight TiO ₂ , SZ 39140, BET specific surface area 80 m) ² /g, particle size 75 to 150 μm), TiO ₂ (Saint-Gobain ST 31119, BET specific surface area 40 m ² /g, particle size 75 to 150 μm), or silicon carbide (SiCat, BET specific surface area 25 m ² /g g, particle size 150 to 250 μm) was impregnated into the support. After impregnation, the material was dried at 120° C. for 3 hours and then reduced at 350° C. for 3 hours under a flow of forming gas (5% H ₂ in N ₂ ).

Example 21

Catalytic performance assay and preparation of FDCA pathway products

Catalyst tests were performed in 1 mL glass vials housed in 96-well inserts placed within high-pressure high-throughput reactors. Diamond, GM, Murphy, V., Boussie, TR, in Modern Applications of High Throughput R&D in Heterogeneous Catalysis, (eds, Hagemeyer, A. and Volpe, A. Jr. Bentham Science Publishers 2014, Chapter 8, 299- 309); See also US 8,669,397, both of which are expressly incorporated herein by reference in their entirety. 10 mg of each powder catalyst was mixed with 0.25 mL of a solution prepared in a 3:2 (wt/wt) dioxane:H ₂ O mixture containing 0.5 M 5-hydroxymethylfurfural (HMF) (6.0% by weight). into the reactor together. The 1 ml reaction vials in the inserts were each covered with a Teflon sheet, a silicon mat and a steel gas diffusion plate (each containing pin-holes to allow gas introduction). The insert was placed in a pressure vessel and it was leak tested under nitrogen pressure. The atmosphere in the reactor was then replaced with oxygen at a target pressure of 200 psig, and the reactor was heated to a target temperature of 120° C., followed by shaking at 800 rpm for 120 minutes. After the reaction was complete, shaking was stopped and the reactor was allowed to cool to room temperature. Samples were prepared for HPLC analysis by sampling from each reactor after diluting with dimethyl sulfoxide (DMSO) and H ₂ O. The reaction products are 5-hydroxymethylfurancarboxylic acid (HMFCA), 2,5-furandicarboxaldehyde (DFF), 5-formylfuran-3-carboxylic acid (FFCA) and 2,5-furandica It was carboxylic acid (FDCA). Each of these products as well as residual HMF was quantified via calibration curves for each analyte by plotting the relative concentrations against the relative detector response against calibration standards and fitting for parabolic expression. The mass balance (MB) is the sum of residual HMF (not shown in Table 3), FFCA, and FDCA pathway products. Results are presented in Table 3.

Table 3. Catalyst composition and performance in oxidation of HMF

Example 22

Performance of various Bi/Pt non-solid supports

Oxidation to FDCA in HMF using various ratios of Bi/Pt on carbon black, zirconia and montmorillonite supports was performed. Four supports were used: Sid Richardson SC159 (carbon black), Orion Asperth 5-183A (carbon black), Zirconia Z1247, and Montmorillonite KA-160. All supports were crushed and sieved to about 75-150 μm from their corresponding extrudates. A single fixed co-impregnation of the solid support was performed with PtONO ₃ +Bi(NO ₃ ) ₃ in 2.0 M HNO ₃ followed by drying and forming gas reduction at 350° C. for 3 h. A single anchoring co-impregnation contained 3 wt% Pt and 0 wt%, 0.1 wt%, 0.3 wt%, 0.6 wt%, 1 wt%, corresponding to Bi/Pt ratios of 0.033, 0.1, 0.2, 0.33 and 0.5 (except control). and 1.5 wt% Bi, or 2 wt% Pt, and 0.1 wt%, 0.3 wt%, 0.6 wt% and 1 wt% corresponding to Bi/Pt ratios of 0.05, 0.15, 0.3 and 0.5. It was performed using % Bi. 5 or 10 mg of catalyst was used for reaction with 0.25 mL of substrate 6.0 wt% (0.50M) HMF in 60 wt% dioxane/40 wt% H ₂ O. The reaction was performed in a reactor at 125° C. for 2 hours and 800 rpm using 200 psi O ₂ (RT). The results are presented in Figures 13-20.

Example 23

Performance of Bi/Pt on various titania supports

Oxidation of HMF to FDCA using Pt and Bi/Pt catalysts was performed on various titania supports. Twelve powdered titania supports were used: Saint-Gobain Norpro ST61120, ST31119 and ST39119, where ST31119 and ST39119 are the same titania support, but with different shapes; Sud-Chemie T-2809 Ti-211 and T-2809 Ti-411; Crystal Global ACTiV DT-S10, DT-51, DT-52, DT-58, DT-W5 (in the form of ultra-fine powder); and Hombicat, Degussa P25 (in the form of an ultrafine powder). Three metal and/or promoter loadings were prepared: 3.0 wt% Pt, 0.30 wt% Bi + 3.0 wt% Pt, and 0.60 wt% Bi + 3.0 wt% Pt. A single fixed co-impregnation of the solid support consisted of PtONO ₃ for 3.0 wt% Pt loading, 0.30 wt% Bi + Bi(NO ₃ ) ₃ + PtONO ₃ for 3.0 wt% Pt loading, 0.60 wt% Bi + 3.0 wt%. For % Pt loading, Bi(NO ₃ ) ₃ + PtONO ₃ in 1.0M HNO ₃ was followed by drying at 120° C. for 2 h and forming gas reduction at 350° C. for 3 h. 8.0 mg of the catalyst was used to react with 0.25 mL of a substrate of 6.0 wt% (0.50 M) HMF in 60 wt% dioxane/40 wt% H ₂ O. The reaction was performed at 800 rpm for 2 hours at 125° C. at 200 psi O ₂ (RT). The results are presented in Figures 21-28.

Example 24

Performance of Bi/Pt on various zirconia supports

Oxidation of HMF to FDCA using Pt and Bi/Pt catalysts on various zirconia supports was performed. Six powdered zirconia supports were used: Saint-Gobain Norpro SZ-1247 and SZ-39140 (Ti); Daiichi Kigenso Kagaku Kogyo Z-2962 (W), Z-2087 (W) and Z-1044 (W); and EG143-59/61-1 (W) manufactured in-house (Morgan Parr & Elif Gurbuzz). Three metal and/or promoter loadings were prepared: 3.0 wt% Pt, 0.30 wt% Bi + 3.0 wt% Pt, and 0.60 wt% Bi + 3.0 wt% Pt. A single fixed co-impregnation of the solid support consisted of PtONO ₃ for 3.0 wt% Pt loading, 0.30 wt% Bi + Bi(NO ₃ ) ₃ + PtONO ₃ for 3.0 wt% Pt loading, 0.60 wt% Bi + 3.0 wt%. For % Pt loading, Bi(NO ₃ ) ₃ + PtONO ₃ in 1.0M HNO ₃ was followed by drying at 120° C. for 2 h and forming gas reduction at 350° C. for 3 h. 8.0 mg of the catalyst was used to react with 0.25 mL of a substrate of 6.0 wt% (0.50 M) HMF in 60 wt% dioxane/40 wt% H ₂ O. The reaction was performed at 800 rpm for 2 hours at 125° C. at 200 psi O ₂ (RT). The results are presented in Figures 29-36.

Example 25

Performance of Bi/Pt on high Bi loading titania and zirconia supports

Oxidation of HMF to FDCA using Pt and Bi/Pt catalysts was performed on various tungstated titania and zirconia supports. The titania supports used were: Saint-Gobain Norpro ST31119, Crystal Active DT-51D, and Crystal Active DT-52, containing 10% WO ₃ by weight. The zirconia supports used were: Saint-Gobain Norpro 61143, containing 17 wt % WO ₃ , tetragonal such as 61143, containing 9 wt % WO ₃ , monoclinic, containing 5 wt % WO ₃ , Zr(OH) ₄ , 8 containing 29 wt% TiO and 29 wt% WO ₃ and Zr(OH) ₄ , containing 9 wt% TiO ₂ ; DKKK Z-1581, containing 10 wt% WO ₃ , Z-2944, containing 20 wt% TiO and 25 wt% WO ₃ ; MEL Cat Zr(OH) ₄ XZO2628/01 with 10% by weight of WO ₃ ; and MP140-28-2 prepared in-house from XZO2628/01 with 10% binder of Niacol ZrO ₂ (AC) & Jusoplast WE-8 (Morgan Parr), containing 9 wt % WO ₃ . 3 wt% Pt was loaded with 0.30 wt% Bi, 0.60 wt% Bi, 1.0 wt% Bi or 1.5 wt% Bi. The supports were treated at 600° C. for 3 hours in air or at 800° C. for 3 hours in air. A single fixed co-impregnation of the solid support was performed using Bi( _{NO 3 ) 3} + PtONO ₃ in 1.0 M HNO 3 followed by drying at 120° C. for 2 h and forming gas reduction at 350° C./3 h. . On a catalyst formed of BiPt/ZrO ₂ (17 wt % WO ₃ ) SZ61143, the catalyst was subjected to gas reduction, followed by air firing at 400° C. for 2 hours. Without being bound by theory, air calcination at 400° C. for an additional 2 hours can oxidize the partially reduced Win support back to WO ₃ . 8.0 mg of the catalyst was used to react with 0.25 mL of substrate of 60 wt % dioxane/6.0 wt % (0.50 M) HMF in 40 wt % H ₂ O. Reactions were performed at 200 psi O ₂ (RT) at 800 rpm for 2 hours at 125 °C. Results are presented in Figures 37-44.

Example 26

Fixed bed reaction with Pt on zirconia support

A fixed-bed oxidation reaction of HMF to FDCA using a Pt catalyst on a zirconia support was performed in a quarter inch reactor. The catalyst comprised 4.2 g of 3.0 wt % Pt/ZrO ₂ 1247 (75-150 μm) in a 23 cm bed length in 1/4 inch OD SS tubing. After preparing the catalyst from a single fixed impregnation with PtONO ₃ , forming gas reduction was performed at 350° C. for 3 h. The ZrO ₂ 1247 support is brittle, and catalyst synthesis results in a 35% loss of material in the desired support size range. The reaction was 116 sccm 5% O ₂ /95% N ₂ (2:1 O ₂ /HMF molar ratio), 174 sccm 5% O ₂ /95% N in the reactor at 125° C. and 1000 psig at an initial rate of 0.80 mL/min. ₂ (3:1 O ₂ /HMF molar ratio), 232 sccm 5% O ₂ /95% N ₂ (4:1 O ₂ /HMF molar ratio). Substrate of 2.0 wt % (0.17 M) HMF in 60 wt % dioxane/40 wt % H ₂ O. Only the lower half of the reactor was heated due to the short catalyst bed length of the ZrO ₂ support. The catalyst showed low activity and very high initial Pt leaching. Results are presented in Figures 45-47.

Example 27

Fixed bed reaction with Bi/Pt on zirconia support

A fixed-bed oxidation reaction of HMF to FDCA using a Bi/Pt catalyst on a zirconia support was performed in a quarter inch reactor. The catalyst comprised 4.2 g of 0.30 wt % Bi + 3.0 wt % Pt/ZrO ₂ 1247 (75-150 μm) in a 23 cm bed length in 1/4 inch OD SS tubing. The catalyst was prepared from a single fixed co-impregnation using Bi(NO3) ₃ + PtONO ₃ followed by forming gas reduction at 350° C. for 3 h. The ZrO ₂ 1247 support is brittle, and catalyst synthesis results in a 35% loss of material in the desired support size range. The reaction was 116 sccm 5% O ₂ /95% N ₂ (2:1 O ₂ /HMF molar ratio), 174 sccm 5% O ₂ /95% N in a reactor at 125° C. and 1000 psig at an initial rate of 0.80 mL/min. ₂ (3:1 O ₂ /HMF molar ratio), 232 sccm 5% O ₂ /95% N ₂ (4:1 O ₂ /HMF molar ratio). Substrate of 2.0 wt % (0.17 M) HMF in 60 wt % dioxane/40 wt % H ₂ O. Only the lower half of the reactor was heated due to the short catalyst bed length of the ZrO ₂ support. The catalyst exhibited higher activity than the Example 26 catalyst, very low Pt leaching, very low Bi leaching, and very low Zr leaching. Results are presented in Figures 48-50.

Example 28

Performance of Pt/Bi, Pt/Te and Pt/Sn on various solid supports

Oxidation of HMF to FDCA was performed using Pt/Bi, Pt/Te and Pt/Sn catalysts on various carbon, carbon/ZrO ₂ , TiO ₂ , ZrO ₂ , ZrO ₂ /TiO ₂ , SiC, and TiC-SiC supports. did The Pt/Bi catalyst comprises 3 wt% Pt loaded with 0.30 wt% Bi, 0.60 wt% Bi, 1.0 wt% Bi, or 1.5 wt% Bi. A Pt/Bi catalyst was prepared on the following supports: in-house prepared carbon 5-183A containing 40% by weight of ZrO ₂ (powder); and Saint-Gobain Norpro TiO ₂ ST31119 (<75 μm) and ST61120 (<75 μm). The Pt/Te and Pt/Sn catalysts contain 3.0 wt% Pt loaded with 0.30 wt% Te or Sn, 0.60 wt% Te or Sn, 1.0 wt% Te or Sn, or 1.5 wt% Te or Sn. include Pt/Te and Pt/Sn catalysts were prepared on the following supports: carbon 5-183 A (<75 μm); Saint-Gobain Norpro TiO ₂ ST31119 (<75 μm), ST61120 (<75 μm); Saint-Gobain Norpro ZrO ₂ SZ1247 (<75 μm), ZrO ₂ containing 40 wt% TiO ₂ SZ39140 (<75 μm); and SiCat SiC DI0478B (150-250 μm), TiC-SiC 40/60 SD0127B2B (powder). The catalyst was synthesized by a single fixed co-impregnation of Bi(NO ₃ ) ₃ , Te(OH) ₆ , or Pt(NO ₃ ) _x containing Sn(oxalate)/H ₂ O ₂ /citric acid, followed by 350 °C Forming gas reduction was performed for 3 hours at 10.0 mg of powder or small particle catalyst was used to react with substrate of 0.25 mL of 6.0 wt % (0.50 M) HMF in 60 wt % dioxane/40 wt % H ₂ O. Reactions were performed at 200 psi O ₂ (RT) at 800 rpm for 2 hours at 125 °C. Results are presented in Figures 51-55.

Example 29

Fixed bed reaction with Bi/Pt on zirconia support

A fixed bed oxidation reaction of HMF to FDCA using a small particle Bi/Pt catalyst on a zirconia support was performed in a 1/4 inch MCR. The catalyst comprised 1.0 wt% Bi + 3.0 wt% Pt/Zirconia 1247 (75-150 μm) (Pablo XRF is 0.92 wt% Bi + 2.82 wt% Pt). The catalyst was prepared by a single fixed co-impregnation with Bi(NO ₃ ) ₃ + Pt(NO ₃ ) _x followed by forming gas reduction at 120° C. for 2 h in air and at 350° C. for 3 h in air. The reactants were started with commercial HMF (Ench Industry), converted to in-house HMF based on H ₂ SO ₄ and then converted back to commercial HMF (Ench Industry). The reaction was 181 sccm 5% O ₂ /95% N ₂ (2:1 O ₂ /HMF molar ratio), followed by 250 sccm 5% O ₂ /95% N ₂ in the reactor at 125° C. and 1000 psig at 0.50 mL/min. (2.8:1 O ₂ /HMF molar ratio). The catalyst comprised 45 cm of 10.1 g 1.0 wt % Bi + 3.0 wt % Pt/Zirconia 1247 (75-150 μm). Substrate of 5.0% HMF in 60 wt % dioxane/40 wt % H ₂ O (Henchi Industries). With commercial HMF, both Bi and Pt leaching were very low after the initial spike. In-house HMF based on H ₂ SO ₄ gives earlier Bi and Pt leaching, but lower Zr leaching than commercial HMF (Nchi Industries). The results are presented in Figures 56-58.

Example 30

Fixed bed reaction with Bi/Pt on zirconia/titania support

A fixed bed oxidation reaction of HMF to FDCA using a small particle Bi/Pt catalyst on a zirconia/titania support was performed in a 1/4 inch MCR. The catalyst comprised 1.5 wt% Bi + 3.0 wt% Pt/Zirconia with 40 wt% TiO ₂ 39140 (75-150 μm). The catalyst was prepared by performing a single fixed co-impregnation with Bi(NO ₃ ) ₃ + Pt(NO ₃ ) _x followed by forming gas reduction at 120° C. for 2 h in air and at 350° C. for 3 h in air. The packing density of the catalyst is about twice that of the carbon catalyst and two-thirds that of the zirconia catalyst. Reactions were run at 0.50 mL/min at 125°C and 1000 psig in a reactor with commercial HMF (Henchi Industries), 181 sccm 5% O ₂ /95% N ₂ (2:1 O ₂ /HMF molar ratio) at 0.50 mL/min. 250 sccm 5% O ₂ /95% N ₂ (2.8:1 O ₂ /HMF molar ratio), 175 sccm 5% O ₂ /95% N ₂ (2.8:1 O ₂ /HMF molar ratio) at 0.35 mL/min, then 250 sccm 5% O ₂ /95% N ₂ (2.8:1 O ₂ /HMF molar ratio) at 0.50 mL/min. The catalyst comprised 1.5 wt% Bi with 46 cm 7.1 g 40 wt% TiO ₂ 39140 (75 to 150 μm) + 3.0 wt% Pt/Zirconia. Substrate of 5.0 wt % HMF (Henchi Industries) in 60 wt % dioxane/40 wt % H ₂ O. Metals in the effluent were measured by inductively coupled plasma mass spectrometry (ICP-MS), with an average of 0.02 ppm Pt, 0.21 ppm Zr detected, and no Bi and Ti detected. No detectable leaching of Bi, Pt and Ti was detected and very low Zr leaching was detected. Results are presented in Figures 59-60.

Example 31

Performance of Pt, Pt/Bi, Pt/Te and Pt/Sn on various solid supports

Oxidation of HMF to FDCA using Pt, Pt/Bi, Pt/Te and Pt/Sn on various solid supports. Catalysts were prepared on the following supports: carbon 5-183A (<75 μm), zirconia 1247 (<75 μm), SiC (SiCat DI0478B, 150-250 μm); Fe ₂ O ₃ (bayoxide E iron red, TO-218, powder), SnO ₂ (prepared in-house from K2SnO3 + HNO3, powder). Four platinum group metal (PGM) loadings were used: 3.0 wt% Pt, or 3.0 wt% Pt doped with 1.0 wt% Bi, 1.0 wt% Te or 1.0 wt% Sn. Pt(NO ₃ ) _x , Bi(NO ₃ ) ₃ + Pt(NO ₃ ) _x , Te(OH) ₆ + Pt(NO ₃ ) _x , Sn(oxalate)/H ₂ O ₂ then Pt(NO ₃ ) The catalyst was synthesized by Alfred M2 loading using _x . 10.0 mg of powder or small particle catalyst was used to react with substrate of 0.25 mL of 6.0 wt % (0.50 M) HMF in 60 wt % dioxane/40 wt % H ₂ O. The reaction was performed at 200 psi O ₂ (RT) at 800 rpm for 2 hours at 125 °C. Results are presented in Figures 61-68.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the relevant art. All patents, applications, published applications and other publications mentioned herein are expressly incorporated by reference in their entirety unless otherwise indicated. In the event that there are multiple definitions for terms herein, the definitions in this section apply unless stated otherwise.

The terms "comprises" and "comprising" as used herein in the implementing language or body of the claims are to be interpreted as having an open-ended meaning. That is, the term should be interpreted synonymously with the phrase “having at least” or “comprising at least”. When used in the context of a process, the term “comprising” means that the process includes at least the recited steps but may include additional steps. When used in the context of a compound or composition or device, the term “comprising” means that the compound or composition or device includes at least the recited features or elements, and may also include additional features or elements.

While preferred embodiments of the present disclosure have been illustrated and described, it will be understood that various changes may be made thereto without departing from the spirit and scope of the present disclosure. Accordingly, it should be clearly understood that the forms disclosed herein are illustrative only and are not intended to limit the scope of the present disclosure.

Claims (141)

Reaction mixture for reducing FDCA pathway products comprising 2,5-furandicarboxylic acid (FDCA) and 5-formylfurancarboxylic acid (FFCA) to hydroxymethylfurancarboxylic acid (HMFCA) contacting with hydrogen in the presence of a heterogeneous reduction catalyst and a solvent under conditions sufficient to form a purified FDCA pathway product.
includes;
The FDCA pathway products purified herein include FDCA, HMFCA, FFCA with less than 10% molar impurity, 5-methyl-2-furoic acid (MFA) with less than 10% molar impurity, and tetrahydrofuran with less than 10% molar impurity. -2,5-dicarboxylic acid (THFDCA);
The solvent is a multi-component solvent comprising water and a water-miscible aprotic organic solvent;
Wherein the heterogeneous reduction catalyst comprises a solid support and a metal selected from the group consisting of Cu, Ni, Co, Pd, Pt, Ru, Ag, Au, Rh, Os, Ir and any combination thereof.
A process for producing purified 2,5-furandicarboxylic acid (FDCA) pathway products. The method of claim 1 , wherein the purified FDCA pathway product comprises greater than 90% FDCA on a molar purity basis. The method of claim 1 , wherein the purified FDCA pathway product comprises less than 5% FFCA on a molar purity basis. The method of claim 1 , wherein the purified FDCA pathway product comprises less than 5% MFA on a molar purity basis. The method of claim 1 , wherein the purified FDCA pathway product comprises less than 0.9% THFDCA on a molar purity basis. The method of claim 1 wherein the yield of reduced HMFCA from FFCA is greater than 25%. The method of claim 1 , wherein the solid support is selected from the group consisting of carbon, zirconium dioxide, titanium dioxide, silicon carbide, silicon dioxide, Al ₂ O ₃ and any combination thereof. The method of claim 1 , wherein the heterogeneous reduction catalyst further comprises a promoter. 9. The method of claim 8 wherein the promoter is selected from the group consisting of Ti, Zr, Cr, Mo, W, Mn, Ru, Cu, Zn, Sb, Bi, Sn, Au, Ag, Pb, Te, and any combination thereof. How to be. The method of claim 1 , wherein the solid support has a surface area of less than 200 m ² /g. The method of claim 1, wherein the water-miscible aprotic organic solvent is tetrahydrofuran, glyme, dioxane, dioxolane, dimethylformamide, dimethylsulfoxide, sulfolane, acetone, N-methyl-2-pyrrolidone (" NMP"), methyl ethyl ketone ("MEK") and gamma-valerolactone. 12. The method of claim 11, wherein the glyme is selected from monoglyme (1,2-dimethoxyethane), ethyl glyme, diglyme (diethylene glycol dimethyl ether), ethyl diglyme, triglyme, butyl diglyme, tetraglyme and polyglyme. A method selected from the group consisting of The method of claim 1 , wherein the water and water-miscible aprotic organic solvent are present in a ratio of water:water-miscible aprotic organic solvent within the range defined by 1:6 to 6:1 v/v. The process of claim 1 , wherein the heterogeneous reduction catalyst and FFCA are present in a weight percent ratio of heterogeneous reduction catalyst:FFCA ranging from 1:0.001 to 1:1 in the FDCA pathway product. According to claim 1,
(a) contacting an oxidation feedstock comprising a furanic oxidation substrate and an oxidation solvent with oxygen in the presence of a heterogeneous oxidation catalyst under conditions sufficient to form a reaction mixture for oxidizing the furanic oxidation substrate to an FDCA pathway product; Generating FDCA pathway products
Further comprising producing an FDCA pathway product by;
wherein the FDCA pathway products include FDCA and FFCA;
No base is added to the reaction mixture during the contacting step (a);
The heterogeneous oxidation catalyst comprises a solid support and a noble metal;
The heterogeneous oxidation catalyst comprises a plurality of pores and a specific surface area ranging from 20 m ² /g to 500 m ² /g or any number therebetween;
The method of claim 1 wherein the solvent and the oxidizing solvent are the same. 16. The method of claim 15, wherein the furanic oxidation substrate is selected from 5-(hydroxymethyl)furfural (HMF), diformylfuran (DFF), hydroxymethylfurancarboxylic acid (HMFCA) and formylfurancarboxylic acid ( A method selected from the group consisting of FFCA). 16. The method of claim 15, wherein the oxidation feedstock comprises a furanic oxidation substrate in a concentration of at least 5% by weight. 18. The method of claim 17, wherein the furanic oxidizing substrate is present in a concentration of at least 10% by weight in the oxidizing feedstock. 16. The method of claim 15, further comprising a second oxidation step,
Here, in the second oxidation step,
(b) a second oxidation feedstock comprising a second furanic oxidation substrate and a second oxidation solvent sufficient to form a second reaction mixture for oxidizing the second furanic oxidation substrate to produce a second FDCA pathway product; contacting with oxygen in the presence of a second heterogeneous oxidation catalyst under conditions and producing a second FDCA pathway product.
contains;
wherein the second FDCA pathway product comprises FDCA and FFCA;
(first) contacting step (a) produces a first FDCA pathway product that is an FDCA pathway intermediate compound alone or together with FDCA;
The second furanic oxidation substrate is the first FDCA pathway product;
(second) no base is added to the second reaction mixture during the contacting step (b);
wherein the second heterogeneous oxidation catalyst comprises a second solid support and a second noble metal. The method of claim 1 , further comprising crystallizing the purified FDCA product to produce FDCA having a molar purity greater than 99%. The method of claim 1 , which is performed at a temperature of 150° C. or less. FDCA, HMFCA, FFCA less than 10% molar impurity, 5-methyl-2-furoic acid (MFA) less than 10% molar impurity, and tetrahydrofuran-2,5-dicar less than 10% molar impurity Purified 2,5-furandicarboxylic acid (FDCA) pathway products including carboxylic acid (THFDCA);
a heterogeneous reduction catalyst comprising a solid support and a metal selected from the group consisting of Cu, Ni, Pd, Pt, Ru, Ag, Au, Rh, Os, Ir, and any combination thereof; and
Multi-component solvents including water and water-miscible aprotic organic solvents
A mixture containing 23. The mixture of claim 22 further comprising hydrogen. 23. The mixture of claim 22, wherein the purified FDCA pathway product comprises less than 10% molar impurity of 2,5-diformylfuran (DFF). 23. The mixture of claim 22, wherein FFCA and FDCA are at least partially soluble in the multi-component solvent. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

Images